CA1090054A - Reactive dyeing system and xylylene diphosphonic acid dyes - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Phosphorus acid substituted chromo-phores are reactively linked to cellulose fibers by means of a phosphorus ester link produced in the presence of a carbodiimide such as cyanamide, dicyandiamide or an alkyl substituted cyanamide or dicyandiamide. Also disclosed are novel xylylene diphosphonic acid dyestuffs of the general formula:

where Dye is a chromophore and dyestuffs of the general formula

Description

~V~V(~i4 BACKGROUND OF THE INVENTION
1. Field of the Invention:
The present invention relates to dyeing of fibers and more particularly to reactively dyed fibers in which a chromophore is linked through a condensation residue to sites on the fiber.

2. Description of the Prior Art:
Dyes are retained in fibers by physical adsorption, salt or metal~complex formation, solution, mechanical retention, or the formation of covalent chemical bonds. Physical adsorption and solution, in which the dye is partitioned between the fiber and the surrounding aqueous phase, are equilibrium reactions, and only by very careful selection of the dyes used, can good washfastness properties be achieved. Salt and metal complex formation are also equilibrium reactions and, though generally the retention of the dye is favored more than in physical adsorption, washfastness may still present a problem. The dyes that are held by mechanical retention (azoics, vats and ~ -sulfurs~ are virtually insoluble in water and show excellent fastness to washing, but have other disadvantages. They are, for example, difficult and expensive to apply; loose dye, which is not easily washed off, may be deposited on the surface, ~ ~

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resulting in low fastness to rubbing (crockfastness~, and the final shade of the dyeing does not develop until completion of the whole dyeing cycle and aftertreatments.
Chemical bonding of dye to fiber for fixation of dye was recognized as early as 1895. The reactive dye systems presently available require that the dyes contain a functional group capable of forming a covalent chemical bond with the fiber.
Fiber-reactive dyes are employed quite widely in coloring cellulosics and proteinaceous fibers. They, of course, exhibit excellent washfastness, resistance to rubbiny, tinc-torial powers, ease of application and leveling. The latter quality is a measure of unifarmity and most important for long dye runs and color matching. The reaction of the dye with cellulosic fibers is basically an esterification or etherifi-cation reaction and is broadly represented as:

Dye ~ O r Cl ~ Cell-OU ~Dye r ~ /-Cell (I) Dye-SO2CH2CH20H ~ Cell-OH 3 Dye-SO2CH2CH20-Cell (II~

"' ' ~ ' " ', "' ' ,, .

- ~9t)(~4 The txiazine reactive group imparts oil solubility characteristics to the high molecular wei~ht dye which hinder and interfere with an aqueous solubllizing group such as -SO3H.
These dyes are unstable and difficult to work with. Most of the reactive dye systems are based upon chemistry where the reaction is effected in alkaline solutions. There are few present reactive dye systems which operate effectively at an ' -acid pH. Such a system is desirable in the dyeing of mixed fabrics such as cotton blends with polyester, wool or nylon, the latter fibers being dyeable by acid dyes. However, acid dyes generally have no affinity for cellulose and usually only find use in dyeing of proteinaceous fibers. Furthermore, since the dye and fiber substrate are coreactive, complete dyeing of the fabric will occur unless speciaI precautions are practiced to localiæe the dye in areas of the fabric by printin~, stenciling or other graphic technique.
The American Cyanamid Company ha$ pu~lished a booklet entitled "Cyanamide", which sets forth a considerable number of reactions of cyanamide and dicyandiamide. Page 32 of this booklet indicates that cyanamide was long known to be a dehydrat-ing agent when wa~med with anhydrous formic acid and in the esterification of lactic or salicylic acid in absolute ethanol.
Note Pratorius-Seidler, G., J. prakt. Ch'em. [2] 21, 129-50 (1880); C.Z. 1880, 245. A number of papers ha~e investigated the reaction of cyanamide with carboxylic acids, and have proposed a mechanism wherein the acid is con~erted to the anhydride by interaction with cyanamide, with formation of - ~U9'30~4 urea, and subsequent acylation of the urea by the anhydride to produce a ureide, which at ele~ated temperatures interacts with the acid to produce an amide. Cyanamide and dialkylcyanamides are also useful in the synthesis of pyrophosphates. Kenner, G. ~, Reese, C.B., and Todd, A.R., J. Che'm.''S'o'c. 1958, 546-51;
C.~. 52, 11072 (1958) indicates that a high energy phosphorus -oxygen bond is present in the presumed intermed;'ate O-phosphoryl-pseudourea.
The use oE cyanamide and phosphoric acid to impart flame retardant properties to cotton and other cellulosic fabrics is well known to the art. For instance, O~Brien "Cyanamide Based Durable Flame-Retardant Finish for Cotton",''Te'xti'le Re's'earch Journal, March, 1968, pp. 256-266 indicates, at page 265, that the reaction of cyanamide and phosphoric acid with cellulose results in a cross-linking of cellulose molecules.
From the properties of the resulting product, it is suggested that the cross-linked cellulose is some type of a dicellulose phosphate ester.
' SUMMAR~ OF'THE''INVENTI'ON
The present invention provides a dye system for dyeing hydroxy substituted substrates in which the reaction can be conducted in acidic to mildly alkaline solutions. The dye system of the invention is a reactive system in which the reactive function is not self-contained in the dye molecule.
Since the dye and fiber require the presence o~ a condensation , . ~ .

.. . . . ..

~090054 agent for reaction, certain dyes such as azo dyes, where the dye is formed by a simple coupling reaction, can be formed via an intermediate on the fabric which can be selectively color developed in discrete locations to form a pattern. The back-ground areas can be fixed to expose or decompose the remaining precursor areas. The dye system of the invention is further simplified in that a single group serves both as an aqueous solubilizing group and as the potentially reactive coupling site to the fiber, thus providing a more simplified synthesis and a less complex and more stable dye molecule and dyed fabric.
The present invention, in one aspect, resides in a method of forming a reactively dyed polymeric substrate, said method comprising:
(a~ contacting a polymeric substrate containing active hydrogen atoms present in the form of alcoholic hydroxyl, amino or thiol groups with a cyanamide compound selected from the group consisting of cyanamide, alkyl-substituted ~yanamide, dicyandiamide, and alkyl-substituted dicyandiamide, wherein the alkyl groups each contain 1-6 carbon atoms, and with a coloring amount of a chromophore-substituted phosphorus acid of the formula:

~iol)n Rm - F - (OH)p (OR)q 1~ 5~

wherein each R is a chromophore, m is 0, 1 or 2;
_ is 0 or 1; _ is 1 or 2; and 5 is 0 or 1; and m -~ p + _ = 3, at least one of m and q being other than 0, at a pH of from about 1.5 to about 9, wherein the equivalent ratio of said cyanamicle compound to each phosphorus acid function of said chromophore-substituted phosphorus acid is at least about 2:1, and (b) heating the contacted substrate to a temperature of at least 200F for a time sufficient to fix said chromophore to said substrate.
In a further aspect, the present invention resides in a method of forming a reactively dyed cellulose textile substrate comprising the steps of:
impregnating a cellulose textile substrate of the formula, RlOH, where Rl is the chain of the cellulose polymer and OH is any hydroxyl group on the chain~in the presence of a carbodiimide selected from the group consisting of cyanamide and dicyandiamide and at a pH of from about 1.5 to about 9, with an aqueous solution containing from 0.1%
to 5% by weight, of a chrc~ophore-substituted phosphorus acid of the formula:
(Il)n rn P (OH)p (OR)q where each R is a chromophore, said chromophore being linked chemically to the P atom, _ is 0, 1 or 2, _ is 0 or 1, p is 1 or 2, and q is 0 or 1, and m + ~ + q = 3, at least one of m and q being other than o, the equivalent ratio of carbo-diimide to each phosphorus acid function of said chromophore-substituted acid being at least about 2:1; said acid being selected from chromophore-substituted phosphonic, phosphinic, T~ I -7a-. ,.: , ~ : ' .

9~)(1S4 phosphonous and phosphoric acids; and heating the contacted sub~trate to a temperature of at least 200~F for a time sufficient to react said acid with said hydroxyl to form a dyed substrate having a phosphorus ester linkage between said chromophore and chain and having the ~ormula~

~O) n ~ :
Il ORl ' R ._ p ¦ \ (OH) (OR)q where z is p~

In s-till anoth.er aspect, the present invention resides in a composition for reactively dyeing hydroxy-substituted cellulose textile substrates comprising an aqueous solution having a pH of ~rom about 1.5 to about 9 and containing at least 0.1~ by weight of a substance selected from chromophore substituted phosphorus acids of the formula : ' ~)n Rm ~ P-- (OH~p .
(OR~q wherein each R is a chromophore, m is O, 1 or 2; _ is 0 or 1;
p is 1 or 2; and ~ is 0 or 1; and m + ~ ~ ~ = 3, at least one of m and q being other than 0; and amine or ammonium salts thereof, and a water soluble carbodiimide selected from the group consisting of cyanamide and dicyandiamide, in which the 2D ratio equivalent of carbodiimide to acid is at least about 2:1. d In a yet further aspect, thi~ invention resides in a method of forming a reactively dyed organic polymeric sub-strate compriæing the steps of:

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(a) contacting a polymeric substrate having reactive groups with active hydrogen atoms selected from amino groups and thio groups in the presence of a carbodiimide with a chromophore substituted phosphorus acid of the formula m I - (OH) (OR)q where each R is a chromophore, m is a, 1 or 2, n is 0 or 1, p is 1 or 2, and ~ is 0 or 1, and m + p +` q =3, at least one of m and ~ being other than 0, and ; :
(b) heating the contacted substrate to a temperature .. . .
~nd for a time sufficient to form a dyed substrate.
In still a further aspect of the invention, there is provided a reactively dyed organic polymeric substra~e of the formula:

~oRl ;
Rm (OR) `~OH)z where each R is a chromophore, said chromophore being linked chemically to the P atom; Rl is the chain of a polymer having reactive groups with active hydrogen atoms selected from alcoholic hydroxyl groups, amino groups and thio groups;
m is 0, 1 or 2; n is 0 or 1; ~ is 0 or 1 and z is 0 or 1; :
and m + p + ~ = 3, at least one of m and q being other than 0.
In our Canadian Patent 1,006,655, granted March 15, 1977, ::
a related invention is disclosed and claimed. According to the invention described in that patent a reactively dyed ~
hydroxy-substituted organic polymeric substrate is formed by ~ :
the steps of: .
contacting a substrate of the formula, Rl~H, where 7c-, :l09~0S~
is the chain of the polymer and OH is any hydroxyl group on the chain in the presence of a carbodiimide with a chromophore substituted phosphorus acid of the formula:

~01 Il n Rm - P - ~OHlp (OR~q where R is the chromophore, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, and ~ is 0 or 1; and heating the contacted substrate to a temperature of at least 200F for a time sufficient to react said acid with said hydroxyl to form a dyed substrate having a phosphorus ester linkage between said chromophore and chain and having the formula~

()n Il / OR
R p ¦ (OH)z ~OR)q where z is p-l.
Also described and claimed in Canadian Patent 1,006,655 are reactively dyed hydroxy-substituted organic polymeric substratera reactively dyed hydroxy-substituted organic polymeric substrate of the formula:

~)n Il oRl :
R P
¦ (OH)z ~OR)q where R is a chromophore group, R is the chain of the polymer, m is 0, 1 or 2, n is 0 or 1, q is 0 or 1 and z is 0 or 1; and compositions for reactively dyeing hydroxy--substituted organic polymeric substrates comprising an aqueous solution containing at least 0.1% by weight of a substance selected from chromophore substituted phosphorus -7d-~ . .
-- ~

~ ~09C~()S~L

acids ~d amine or ammonium salts thereof and a water soluble carbodiimide in which the ratio equivalent of carbodiimide to acid is at least about 2:1. The invention to which said Canadian Patent 1,006,655 pertains îs concerned particularly with the dyeing of cellulosic su~strates.
The present invention is an outgrowth from, and an extension of, the invention as described and claimed in Canadian Patent 1,006,655.
The dye system of the present invention results in reactively dyed fabrics by immobilization of a dye as a cellulose phosphorus ester according to the following illustrative reaction:

(Il)n (¦¦)n OR' Rml-(OH)p + R'OH ~ CDI ~Rm~ ~ CDIX
(OR)q (OR) Z

where R is as defined above, R'OH is cellulose, CDI is a carbodiimide, CDIX i~ a CDI residue or by-product, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, q is 0 or 1 and z = p-l.
Thus, a chromophoric grouping (R) linked chemically to a phosphorus acid such as phosphonic, phosphonous, phosphinic or phosphoric acid, reactively dyes cellulose 23 (R'OH) with the aid of a carbodiimide condensing agent (CDI).
Cyanamide which is a suitable carbodiimide, allows for a rapid esterification of phosphorus acids with alcohols. The by-product, CDIX, is urea. Thus, where R is a chromophore and R'OH is cellulose, a fiber reacted dye compound is formed -7e-lV9(1~VS~

with cellulose. This results is a substantial and washfast dyeing of cotton and other cellulosic or hydroxy containing substrates. Cellulose esters of phosphonic acid dyes are ~ound to be the most stable to heavy-duty alkaline detergents. The reaction of phosphonic acid dyes would proceed as follows:
O ' O
R-P-OH + R'OH + CDI ~ R-P-OR' + CDIX
OH OH
The fabric or fiber sys~em of the invention proceeds by forming an aqueous solution of a chromophore or precursor thereof linked chemically to a phosphorus containing acid.
The solution generally contains at least 0.1% of the dye and generally no more than 10% by weight of the dye depending on the intensity of the chromophore and the shade desired. The dye concentration is generally between 0.1 and 5% by weight and the concentration of reacted dye on the fabric is believed to be in the range of 0.01 to 0.05 weight percent, although much greater concentrations of dye on the fabric can be employed, e.g., up to even 5.0 weight percent, or more; 10 4 to 10 mol. percent.
; The pH of the solution is generally about 3-4 but can be varied from about 1.5 to 9. Lower pH can be provided by addition to the impregnation bath of 1%-5% of an acid which is non-volatile at the cure temperature, and does not cause undue degradation of the substrate, such as a phosphoric acid, lower alkyl phosphonic acid or chloroacetic acid. This appears to improve the efficien~y of the dye immobilization since less dye is found to wash out after cure. The amount of carbodiimide is usually increased in a bath containing added acid. Higher pa haths may be utilized containing salts . ~ ~

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lO~?(~S4 which are converted to the acid form during cure such as fugitive amine salts, or ammonium salts of the phosphorus acid chromophore~ Higher pH baths may be necessary in certain situations which present corrosion problems, or have mixed fiber systems or fibers which would be excessively degraded at low pH.
Generally, in the bath the molar equivalent ratio of the diimide to each phosphorus acid function is at least about 2:1. Curing is generally conducted at a temperature of at least 200F and generally below 4~0F. Preferably, the fabric may be preliminarily dried at a temperature below 200F before cure. The cure time can be varied ~rom the order of seconds to hours depending on the temperature, dye concentration and fiber being colored.
The reactive dye system of the invention is general-ly applicable to substrates containing available hydroxyl groups such as cellulose, particularly cotton~and may be practiced on fibers, films, yarns, cords, threads, paper, fabrics, non-woven or wov~n, knitted; or other types including pile fabrics, velvets, knitted fabrics, corded webs or webs formed by a random webber.
The water-soluble condensation agent assists in the - formation of the phosphorus ester linkage between the chromo-phoxe, R, and the cellulose substrate, R'OH. The agent is preferably a water-soluble carbodiimide such as cyanamide or dicyandiamide.
The impregnating bath may also contain minor amounts of conventional additives or assistants such as anti-migrating agents, Glauber's salt, or wetting agents. Compatible thick-eners may also be present.
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The dyes that can be utilized in the dye immobiliza-tion process of the invention can be of diverse type and structure. The dye may be an anthraquinone, phthalocyanine, mono-azo, polyazo, benzanthrone, pyrazolone, naphthoquinone, triarylmethane or cyanine type that is modified to contain a phosphorus acid group to impart water-solubility and to provide a reactive site for attachment to the hydroxyl groups on the substrate. The dyes may contain other aqueous solubilizing groups such as sulfonate and may contain other substituents that do not interfere with aqueous solubility characteristics or the dye immobilization esterification reaction.
Many of the phosphorus acid substituted dyes utilized in the process of the invention are known materials readily available in the art, and have been used to direct dye wool and other proteinaceous fibers. Suitable dyes are disclosed in Belgium Patent No. 570,326, British Patent No. 455,092 and United States Patent Nos. 2,596,660 and 2,7991701. Analogues of many sulfonated dyes can readily be synthesi~ed in the phosphono form by substituting the phosphono analog for the sulfono-containing compound during synthesis.
The process of the invention may be readily adapted so that it can be carried out in commercially available machinery used for dyeing or textile printing processes and for continuous o-.- non-continuous variations of such processes. The fibrous or sheet material may be impregnated wlth the dyestuff solution and then subjected to curing by heating, for example, in a hot flue dryer, an oven or a stenter. The impregnation may be carried out for example by padding material with an aqueous solution containing the dyestuff and curing agent. The dye treatment may also be carried out by textile printing methods, ~ "; 10 . . . . . . . .. .. . . . . . ..

D9(9(~5~L

for example, by locally treating the textile with a solution containing the dyestuff and condensation agent and thereafter subjecting the printed material to an elevated temperature for curing. Alternatively a phosphono-substituted primary agent may be coupled to the cellulose and thereafter coupled to an azo chromophore component.
The invention will now become better understood by reference to the following detailed description when considered in conjunction with the specific examples of practice. It is to be understood that these examples are presented solely for purposes of illustration and not by way of limitation, and alternative materials may readily be substituted without depart-ing from either the spirit or scope of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following example illustrates the synthesis of a phosphono analog of CI Acid Yellow No. 11, a pyrazolone dye:

8.7 grams of 3-aminobenzenephosphonic acid and 5.3g of Na2CO3 were added to 100 ml of H2O and cooled to 15C.
3.7g of NaNO2 in 10 ml of H2O were added to yield a brown solution which was slowly poured with stirring into 21 ml of concentrated HCl containing 60~ of ice. The mixture was stirred for 15 minutes and gave a positive response to the starch - KI
test.
The diazotisation method is based on Vogel, "Practical Organic Chemistry" (1951~, p. 596, and follows the following reaction se~uence:
NH2 N=NCl +NaUO2 + PCl Na2CO3 ~ O(OP)2 (III) ~Q900Si~lL

Coupling of the diazotized intermediate ~III) is based on British Patent No. 753,771. The solution containing the intermediate (III) was added to a solution containing 12.7g (1/20 mole) of 3-methyl-1-(p-sulfophenyl)-2-pyrazolin-5-one and 10g of sodium acetate in 100 ml of M2O. The pH of the second solution had been adjusted fxom 5.3 to 7.0 with NaOH.
After stirring for 15 minutes the pH was 2.0 and there was no evidence of precipitation. On addition of isopropanol, a yellow powder was precipitated which after separation and drying in a vacuum oven yielded 13g. Coupling proceeded according to the following reaction:
N=N-Cl ~ ~(~)2 CH P~O(OH)2 C

~,~N-C611453Na ~_ ~e~

The following example illustrates the synthesis of a bis phosphono, bis-azo dye.

3-Aminobenzenephosphonic acid was diazotized according to the procedure of Example 1 using 13 ml of concentrated HCl.
18.0g (1~20 mole~ of the mono-sodium salt of 8-amino-1-naphthol-3,6-disulfonic acid was suspended in 50 ml of H2O and the pH was adjusted from 2.3 to 7 with NaOH~ This solution was added to the diazotate to form a dark red solution having a pH

of 2.5.
Alkaline coupling was p~acticed according to Vo~el, supra, p. 597.

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The red solution precipitated on standing and was adjusted to pH 7 with NaOH. 40 ml of a 10~ NaOH solution was then added and cooled to 5C. A second preparation of diazotate was then added to form a blue solution having a pH of 7.4.
After 15 minutes the pH was adjusted to a pH of 2 with HCl~ The dye was precipitated with isopropanol to yield 40 grams of black powder having the formula:

~N=II~_N=N ~

PO(OH)2NaO3S SO3Na PO(OH)2 The pyrazolone yellow dye of Example 1 was used to dye cotton fabrics according to the following procedure.
E~AMPLE 3 A pad bath was prepared containing 5~ of the pyrazo-lone yellow dye, three molar equivalents of cyanamide (1.33 weight pexcent) and 0.1~ "Triton X 100*" (Rohm & Haas - octyl phenoxy polyethoxy ethanol - non-ionic wetting agent). The bath had a pH of 2.9. Samples of print cloth fabric were padded at 40 psi, and then oven dried for five minutes at 150F
except for one fabric that was air dried at room temperature.
One sample of fabric was cured for five minutes at 320F. An oven dried fabric was cut in half for color comparison. All but one one-half of the oven dried fabric were washed for eight minutes with heavy-duty detergent, dried and then ironed. The air-dried fabric was colorless, the oven dried fabria was colorless, whereas the cured fabric had a bright lemon yellow color with some washoff by comparison with unwashed ~abrics.
The colored fabrics were boiled for one hour in 3~ K2CO3 with some color lost. The final color was a pastel yellow shade of the original bright yellow color.

*Trademark ' . : ' - lO~OOS~

Since the fabric subjected to air drying lost all color on washing, it is apparent that the dye was not substan-tive. It is quite unexpected that the ester linkage of the fixed dye is stable to hot detergent alkaline medium since it would be expected that the phosphorus ester moiety would hydrolyze and rupture the dye attachment.
The blue dye of Example 2 was utilized to color cotton fabric according to the following procedure:

A pad bath was prepared containing 5~ of the blue dye plus 6 molar equivalents of cyanamide (1.73~) and 0.1% of , Triton X 100. The p~l of the bath was 2.6. Samples of cotton fabric were treated, dried and cured as in Example 3. After washing, the air-dried fabric was almost colorless. The oven-dried fabric was a very pale blue, whereas the cured fabric was a very dark navy blue. There was some slight washoff by comparison with the unwashed fabric. The warp shrinkage was -3.75% whereas the fill shrinkage was +0.75~. After the fabric was boiled for one hour in 3% K2CO3, the final color was a dark purple.
It was then attempted to fix the dye of Example 1 on fabric using heat without the presence of a carbodiimide.

A bath was prepared, containing 5% by weight of the I~ J
pyrazolone yellow dye of Example 1, plus 0.1~ Triton X 100.
The pH of the bath was ~.9. The bath did not contain any carbodiimide or equivalent material.
Samples of cotton fabric were padded at 40 psi, dried fox five minutes at 150F and cured for five furthar minutes at 320F, washed in heavy-duty detergent and ironed. The -- 1~ --~ ~' . .

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fabrics contained only a trace of yellow color. A dye and heat step at curing temperature is not capable of fixing the dye on the fabric.
It was then attempted to fix on fabric the dye of Example 1 by means of a pad bath containing urea.

A bath was prepared containing 5~ by weight of the pyrazolone yellow dye of Example 1, 0.1~ Triton X 100 and 1.9%
urea (3 molar equivalents). The pH of the bath was 2.9.
Samples of cotton fabric were trated as in Example 5 and the samples retained no more color than those of Example 5 showing that no dye immobilization occurred by this procedure.
It was then attempted to fix the dye of Example 2 on fabric using heat or urea in the absence of a carbodiimide.

Two baths were prepared, one containing 5~ of the ll 11 blue dye of Example 2 plus 0.1% Triton X 100 and the other additionally containing 2.5~ urea ~6 molar equivalents). The p~ of the first bath was 2.65 and that of the second bath with urea was 2.70. Samples of cotton fabric were padded at 40 psi, dried for five minutes at 150F, cured for five minutes at 320F, washed in heavy-duty detergent and ironed. Only a trace of blue remained in the fabrics. Colors were all about the same.
The Eollowing example shows the use of polyvinyl alcohol and phosphoric acid as adjuvants to the coloring bath:
EXA~PLE 8 ':
A pad bath was prepared containing l~ by weight of the blue dye of Example 2, l~ H3PO4, 1.6% cyanamide and 6 milliliters of 4% polyvinyl alcohol. No wetting agent was .~ j . .

. ' : ' ' .
.

~9~:)VS4 added. The pad bath was used to treat 100% cotton cloth and 50-50 cotton polyester cloth, according to the procedure of Example 3. The cloths showed good color retention and sta-bility with very little washoff and very good resistance to boiling K2CO3. A similar bath containing 4% "Cellosize*" in place of polyvinyl alcohol gave a similar result and also imparted some blue color to glass cloth.
The following example illustrates the use of dicyan-diamiae in place of cyanamide.

A pad bath was prepared containing 1.5% by weight of ~ -the yellow dye of Example 1 and 1% of dicyandiamide. (0.8%
would be a molar ratio of 1:3), Samples of cotton cloth were treated according to the procedure of Example 3. After wash-ing, the dye iNmobilization was essentially the same as ~he ~
cyanamide treated fabrics of Example 3. ~-The following example illustrates preparation of the benzyl phosphonic analog of the dye of Example 1.

p-Aminobenzyl phosphonic acid was coupled with the sulfophenyl pyrazolone utilized in Example 1 utilizing 9.4 grams of the benzyl acid (0.1 mole) in place of 8.7 grams of the phenyl acid. The pH was finally adjusted to 3.0 with HCl and the solid precipitated with isopropanol, presumably as the monosodium salt having the structural formula:

*Trademark of Union Carbide Corporation for hydroxyethyl cellulose and/or carboxymethyl cellulose.

~10900S~9L
o CH3 1 ~ N=~ ~ C~2 - ~ - ~

O OH

S03Na .
The dye exhibited similar behavior when utilized to color cotton fabric samples according to the procedure of Example 3.
The following experiment illustrates the preparation and use of the ammonium salt of the dye of Example 1 at higher pH.

An ammonium salt of the yellow dye of Example 1 was prepared by dissolving the dye in an aqueous NH40H solution and evaporating the solution to dryness.
A padq bath was prepared containing 1% of the ammonium salt dye, 0.3% cyanamide and 0.25% "Alipal CO 436*" (nonyl phenoxy polyethoxy ethanol-sulfated, NH4 salt). The pH of the bath was 5.8. The bath was applied to fabric and cured as in Example 3. The dye immobilization was substantially the same as in Example 3.

An acid pad bath was prepared containing 1% of the sodium salt of the phenyl dye of Example 1, 0~25% of "Alipal**"
and 3% of H3P04 and 4.5% of cyanamide which represented a molar equivalent ratio of 3:1 of the cyanamide to the combined dye and acid. The pH of the pad bath was 1.8.

*Trademark **Trademar~ for a series of anionic surfactants containing alkylphenol and ethoxy groups in the molecule.

.. . . . . .

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: ~IV9~)1)54 Samples of fabric cloth impregnated, cured and washed according to the procedure of Example 3 showed very little washoff. U.V. analysis of the cloth indicated about 75~ dye fixation.

Methyl phosphonic acid (MPA) was substituted for the H3P04 of Example 12 and the cyanamide content was reduced by 1.3% to adjust the MPA/cyanamide molar equivalent ratio to 1:2.
The pH of the bath was 1.8. Samples of fabric, impregnated, cured and washed according to the procedure of Example 3 again demonstrated very little washoff. A sample of fabric which was air-dried before cure to minimi7e miyration showed some-what improved color retention.
The following experiment shows the necessity of a phosphorus acid group in the dye molecule.
EX~MPLE 14 A pyrazolone dye was prepared utilizing metanilic acid in place of the 3-aminobenzenephosphonic acid of Example 1. A bath was prepared containing 1% of the sulfonated dye, 3~ H3PO4, 0.25~ "Alipal*" and 4.5~ cyanamide. The pH of the bath was 1.75. Samples of fabric impregnated, cured and washed according to the procedure of Example 3 showed extreme washoff demonstrating that little or no dye was fixed.
Fixation and immobilization of dye by formation of a phosphorus acid ester linkage was further confirmed by the following experiment.

A solution of 5~ 3-aminobenzenephosphonic acid con-tainil~g 3 molar equivalents of cyanamide was utilized to impregnate cotton cloth. The cloth was cured at 320F for *Trademark for a series of anionic surfactants containing -alkylphenol and ethoxy groups in the molecule.

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five minutes to couple the amine base to the cellulose throughthe phosphono-linkage.
The cellulose-coupled amine base was then subjected to diazotization with the NaNO2-HC'l solution of Example 1 to form a diazonium sal~. A portion of the cloth was exposed to light to decompose the diazonium salt. The fabric ~as then immersed in a solution of the sulfophenyl pyrazolone utilized in Example 1 and dried and washed. Color was only retained in - the nonexposed areas, confirming the phosphono-ester linkage as the immobilization mechanism.

A copper phthalocyanine substituted with phosphonic acid and sulfonic acid groups was prepared by heating an inti-mate mixture of triammonium 4-sulfophthalic acid (llg), mono-potassium 4-phosphonophthalate (llg), urea (20g), cupric chloride dihydrate (3g), and ammonium molybdate (0.25g) at 250C. The product was purified by washing with hydrochloric acid and drying in a vacuum oven at 60C.
A bath was prepared containing 1% of this product, .' .
1% H3PO4, 4.4~ cyanamide and 0l25% Alipal. The pH of the bath was adjusted to 2.5 with triethanolamine. Samples of fabric impregnated, cured and washed according to the procedure f 1` ' Example 3 were a greenish-blue color.
The present invention provides a novel acid system for the fast dyeing of hydroxy fibers. The reactively dyed - fibers exhibit good color and are stable to hot basic media.
The dye system of the present invention provides a further advantage since the dye can be recovered from the bath by precipitation on a calcium substrate such as lime, CaCO3 or marble and can be regenerated by acid.

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..
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-The results obtained hereinabove indicate that the process of reactively dyeing textiles and other substrates has broad applicability. The process of the present invention may be broadly applied to many substrates having an active hydrogen atom according to the well-known Zerewitinoff test (J Am. Chem.
S _ , 49, 3181 (1927)~. Especially preferred are substrates having alcoholic hydroxylt non-phenolic) groups, amino groups, or thiol groups. That is, the reactive site on the substrate may have the formula -OH; -NH2(amino); -N~I--(amino); or -SH.
Thus the process of t~e;`present invention-results in the ~lxation of phos-~horus-containin~ dyestuffs on rayon. The fixation is-obtamed with wool but t~e depth of-shade-is not as<~x~ as with~rayon.~ Fixation of;the dye~tuff is also obta;ined with nylon,~but-the depth of shade is~somewhat-~inferior to that of wool. Of the substrates having Zerewitinoff-active hydrogen atoms, those compounds having hydroxyl groups are greatly preferred, especially organic polymers having hydroxyl groups.
While the substrate may be in the form of cast or other massive articles, it is greatly preferred that the substrate be a textile fabric or a textile yarn, filament or fiber.
The results obtained with cyanamide and dicyandiamide suggest that cyanamide compounds of the general formula 'l N - C - N
x2/
wherein Xl and x2 are hydrogen, lower alkyl, or together are N(X3)2 N(X )2 `--` 109V()S4 wherein each X is independently hydrogen or lower alkyl, can be used in the process of the present invention. Thus, methylcyanamide, dimethylcyanamide, ethylcyanamide, diethyl-cyanamide, butylcyanamide, dibutylcyanamide, and other cyan-amide compounds falling within the scope of the above formula disclosed in the aforesaid American Cyanamid Company "Cyanamide"
booklet, may be used in place of cyanamide or dicyandiamide.
Compounds of the above general formula may exist in tautomeric form and these -tautomers are intended to be included in the general formula.
The dye, the fiber, and the cyanamide compound can be brought together in any particular order. Normally, the dye and the cyanamide compound, together with any conventional additives or assistants, will be in the form of an aqueous solution, which is padded or otherwise applied to the substrate.
At least a coloring amount of the dye will be reacted onto the substrate.
As mentioned hereinabove, it is possible to form the dyestuff on the fabric essentially "in situ", by coupling a phosphono-substituted compound to the cellulose and thereafter coupling that compound to an azo chromophore compone~t or other chromophoric group. Alternatively, the phosphorus-containing dyestuff could be applied to a textile fabric which is then subjected to an aftertreatment with the cyanamide compound. Regardless of the techni~ue actually used, it is clear that the thrust of the present invention resides in contacting a polymeric substrate containing ~erewitinoff-active hydrogen atoms, especially alcoholic hydroxyl, amino, or thiol groups, with a cyanamide compound and with a chromophore-substituted phosphorus acid or a chromophore precursor-substituted phosphorus acid, and heating the contacted ~0900$~
"

substrate to an elevated temperature to fix the chromophore or chromophore precursor to the substrate.
Mixtures of substrates, dyes, and/or cyanamide compounds may be used if desired.
The addition of phosphoric acid to the impregnating bath appears to improve the effic:iency of the dye immobiliz-ation, but can have the undesirab:Le effect of reducing the strength of the fabric by as much as about 50~. Dyes contain-ing two phosphonate groups or other phosphorus acid groups have been found to have an efficiency of greater than 90%, when affixed to cotton or another suitable substrate by the use of cyanamide or dicyandiamide, without using any phosphoric acid in the.dyebath. Since no phosphoric acid is added to the dyebath, the fabric essentially loses no strength during the dyeing process. Thus, where the strength of the textile fabric must be maintained, and high coupling efficiencies of the dye-stuff achieved, the use of the dyestuffs containing two or more phosphorus acid substituents is often greatly preferred.
However, recent work has established that monophos-phonate dyestuffs can produce excellent fixation on substrates,using the process of the present invention, at a pH of about 5.
To achieve this pH, it is preferred to add about 0.125 to about 0.25 weight percent of phosphoric acid to the dyebath.
Thus, broadly the amount of acid that can be used in the dyebath ranges from about 0.1 to about 5 weight percent.
Example 4 hereinabove relates to using a di(ph~s-phorus acid)-substituted dyestuff. Additional examples of using such dyestuffs are set forth below.

., : ' ' . ' ~ . . ' '' ' : .

OOS~

H acid (81% pure, 43.5y, 0.1 mole) of the formula:

S0 ~ S~3H

was suspended in 300 ml water and 100g ice and the pH adjusted to 6 with sodium hydroxide solution. Sodium acetate (3 9g, 0. 3 mole) was added, followed by m-chlorosulfonylbenzenephosphonic acid (30g, 0.12 mole) in portions over 10 minutes, the temper-ature being maintained at 10C and the pH at 6. The solution was stirred for three hours in an ice bath, and then sodium -carbonate (25g) was added.
To this solution was added a diazotized solution of m-aminobenzenephosphonic acid. The combined solutions were -stirred for 1 hour, then concentrated hydrochloric acid (400 ml) was added and the solution filtered to yield~ a red dye with the structure: :
~ , .

P ~ ~ N=N
~ PO(OH)2 ", EXAMPLE 18 :
.
This and the following three examples relate to the production of or~n~e dyesr using, as the starting compound, J
acid of the ~ormula:
OH
~ ~.

- .. .
: . ' :

:1(19~30S9~

in place of the H acid. Example 17 was repeated, replacing the H acid with J acid, producing an orange dye of the formula: . O~
~ ~ PO~O~ 5 ro(o~)~ s~ HSO~ ~

:
Example 18 was repeated, but using the N-methyl derivative of ~he J acid, to produce an orange dye of the formula: 0 ~ SO~`~

EXAMPLE 20 I:
Example 18 was repeated, but the m-chlorosulfonyl-benzenephosphonic acid was replaced by benzoyl chloride, and the diazotized solution of m-aminobenzenephosphonic acld was replaced with a diazotized solution of o-amino-p-xylylenedi- ¦~
phosphonic acid, to produce an orange dye of the formula:
C~l PO(~ ~

Cll,P~rol~5~;~N

Example 19 was repeated, but the m-chlorosulfonyl-benzensphosphonic acid was deleted, and the diazotized solu-tion of m-aminobenzenephosphonic acid was replaced with a diazotized solution of o-amino-p-xylylenediphosphonic acid, to produce an orange dye of the formula:

; ~ - 24 - .:
~i~' ; .

` 1~9~S~
, .

C l~ PO (OH);~, Ol~

¢~ 50~tV H C
CH,~,roH) ~XAMæL~ 22 Following the procedure of Example 21, an orange dye was made by treating ~ -naphthol with diazotized o-amino- .
-p-xylylenediphosphonic acid, and the resulting dye had the formula:
o~ ~H~Pr~

~ 1 poft~H)a Example 22 was repeated, replacing the ~ -naphthol with F acid, of the formula: I, ~0 ~ 5~

., . .

, ' ' ~ : ~ : , .. : .. .. ~ .

V9U(:)S4 , resulting in an orange dye of the formula:
OH CH2PO(OH)2 N=N ~

CH2PO(OH)2 o3 EXAMPLE 2~
Bromaminic acid ~89.9~ pure, 132 g, 0.315 mole), p-amino benzylphosphonic acid (65 g, 0.345 mole), and cuprous chloride (12 g) were stirred in water (800 ml) and ethyl alcohol (200 ml), and sodium carbonate (160 g, 1.5 mole) added in portions. The solution was then heated to 50C, and stirred at 45-50C for 18 hours. The reaction mixture was cooled and poured carefully into concentrated hydrochloric acid (300 ml), and then filtered. The residue was recrystallized from aqueous hydro-chloric acid to yield a blue dye of structure:
O NH

~C~2P(~1)2 EXAMPLE 25 ~ -Example 24 was repeated, but the p-aminobenzylphos-phonic acid was replaced by an equimolecular amount of . . ..

~ 9V05~
o-amino-p~xylylenediphosphonic aci~d; to- produce a blue dye of the structure:

( )2 O NH

CH2PO(OH)2 o-Amino-p-xylylenediphosphonic acid (28 g, 0.1 mole) , was dissolved in water (150 ml) and sodium carbonate (21.2 g, 10 0.2 mole) ~added. Sodium nitrite (7.~ g, 0.107 mole) in water ~, (40 ml) was added, and the solution was poured into a mixture of -concentrated hydrochloric acid (50 ml) and ice (100 g). The '' so~ution was stirred at 5 for 20 minutes and then the excess nitrous acid d~stroyed`with sulfamic acid. This solution was, added,i~to a solution of 3-methyl-1-(p-sulfophenyl)-2-pyrazolin-5-one (25.4 g, 0.1 mole) in water (300 ml) containing sodium carbonate,(50 g), and stirred for 1 hour at 5C~ The solution was acidified with hydrochloric acid and from it was isolated the yellow dye:

CH2PO(OH)2 H~f r CE2PO:1-3}~

. . .
. ., ~ ' : .
. ., . ~ .

- ~1)9V059~

A pad bath was prepared containing 1% of the orange dye of Example 23, 2% of dimethylcyanamide (about 15 molar equivalents) and 0.1% "Triton X100". Samples of a multicomponent fabric containing discrete bands of wool, viscose rayon, silk, nylon, cotton, and "Dacron*" were padded at 40 psi~ oven dried for 2 minutes at 180F and cured for 1.5 minutes at 390F. The fabrics were washed in detergent, rinsed and dried. Under these conditions, the wool was only slightly tinted and the "Dacron" unaffected. The rayon and cotton were dyed a bright orange, the nylon was dyed pink, and the silk was dyed a darker shade of orange than the cellulosic fibers.

*Trademark of DuPont for polyethylene terephthalate polyester fiber.

An aqueous dye solution was made, with the solution containing 1% by weight of the orange dye of Example 18, 1% by weight of cyanamide, and 0.1% by weight of a surfactant ("Triton X100"). Rayon, nylon and wool fabrics were immersed in the dye solution, dried for five minutes at 180~F and cured for 90 seconds at 390~F. After one home laundering the dyed samples showed significant dye fixation, with the rayon dyed the most strongly, f~we~c in order, by wool and nylon. -Separate aqueous dye solutions were prepared with each of the orange dyes of Examples 19, 20 and 23, each solution containing 1% by weight of the dye and 1% by weight of cyanamide.
Separate cotton fabrics were then immersed in the respective dye solutions and then dried for five minutes at 180F and thereafter cured for 90 seconds at 390F. After one home laundering all of the dyed samples showed excellent dye fixation.

:' , ' : ' : :

-- 109VOS~

An aqueous dye solution was made with the solution containing 1% by weight of the yellow dye of Example 26 and 1%
by weight of cyanamide. Cotton fabrics were immersed in this dye solution, dried for five minutes at 180F and cured for 90 seconds at 390F. After one home laundering the dyed samples were a bright yellow color and had excellent dye fixation.

An aqueous dye solution was made, containing 0.5% by 10 weight of the blue dye of Example 25 and 3% by weight of dicyandiamide, this solution having pH of 2. Cotton fabrics were immersed in the dye solution, dried for five minutes at 180F and cured for 90 seconds at 390F. After one home laundering the fabrics were dyed a bright blue and the dye fixation was excellent.
EXAMoeLE 32 An aqueous dye solution was made containing 0.5% by weight of the blue dye of Example 25 and 1.25% by weight of cyanamide, the pH of said solution then being adjusted to a level of 3 by the addition of ammonium hydroxide. Cotton fabrics were immersed in the dye solution, dried for five minutes at 180F and cured for 90 second~. After one home laundering the fabrics were dyed bright blue and the dye fixation was excellent.

In a fashion generally similar to that of Example 28 above, cotton swatches were dyed in aqueous dye solutions prepared from each of the dyes of Example 21 (orange), 22 l l -~orange) and 24 (blue). All of the dyed swatches showed excellent dye fixation after the home laundering.

.. . .

- ~9~os~

COMPARATIVE EXAMPLE A
Example 28 was repeated, except the cyanamide was omitted. After one home laundering, the dyed fabrics were only tinted a very pale orange (an indication of little if any dye fixation).

, . . . . . . .

~ v~)s~

Additional classes of phosphorus-containing dyes can be readily prepared, following the procedures of Examples 17-21 and 23, but replacing the H, J and F acids with the dye intermediates disclosed in U.S. Patents:

2,847,458 2,799,701 2,717,9~6 and 2,553,417 Additional phosphorus-containing dyes which rnay be used in the practice of the present invention are disclosed in the following patents:
Belgium 563,439 U.S. 2,326,047 ~i U.S. 3,339,999 . U.S. 2,183,998 - U.S. 3,202,550 British 970,585 11 West German 1,042,523 Additional dyes which can be produced following the procedure of Example 21, but with different naphthylenic starting materials, are of the formulae~
~ , - P~(~
- ( ' i~ ~
fZ T~ ~ 1 . . ¦ HO3S
., . pO t~) . , .

, and .

~o~ s~

T'(~H~2 ' , "
c ~

¦ H03S CvC~
J

It is believed that the dyes of Examples 17, 18 and 19 are novel. The~results obtained with the dyes of these examples suggest that a new dye family of the class Dye-N-SO ~
2 ~ PO(0~)2 ;

wherein R is hydrogen or lower alkyl, has been discovered.
These dyes, especially those containing two or more phos-phonate groups, work very well in the process of the present invention.
Of the various phosphorus-acid-substituted dyestuffs disclosed hereinabove, those dyestuffs substituted with more than one of said phosphorus acid radicals are particularly preferred, due to the excellent fixation obtained.
In the latter regar~, the dyes containing more than one phosphonate group have, as mentioned hereinabove, been found to be particularly preferred. The phosphonate sub-stituents may be located at any point on the dye molecule, at generally proximate positions or at positions further removed from one another such as at the distal ends of the dye moiety.
Of the various phosphorus-acid-substituted dye-stuffs disclosed hereinabove, those dyestuffs substituted with one or more phosphonate radicals are particularly :- ,J, .~ .

)900S~L
preferred, due to the ease oE dyeing and excellent durability obtained.
The results obtained herelnabove indicate that chromophore-substituted phosphorus acids broadly of the formula:

(Il)n R - P - (OH)p (OR)q wherein each R is a chromophore, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, and q is 0 or 1, and m + _ t q = 3, and wherein at least one of m and q is other than 0, may be used in the process of the present invention. Chromophore-substituted phosphorus acids having hydrocarbon substituents on the oxygen atom (in addition to the chromophore) are not preferred, due to the decreased reactivity of these compounds, as well as the greater effort and expense in manufacturing same. However, it will be appreciated that such compounds may be used to replace part or all of the chromophore~substituted phosphonates or phosphates or similar compounds. Normally, only one chromophore will be attached to the phosphorus atom, eithex directly or indirectly (that is, it is preferred that the sum of m and ~ is 1, for both the formula above and of page 7 hereinabove), and it is preferred, as indicated hereinabove, that the chromophore carry two or more phosphorus acid groups.
The present invention also includes novel xylylene diphosphonic acid dyestuffs of the general formula:

~10~30~)S~L
.

Dye ~

wherein Dye represents a chromophore~ preferably an azoic chromophore. Such dyestuffs offer two potentially reactive sites when used in the process described herein, and thus generally result in high levels of fixation of the dyestuff on the substrate.
~: In addition to the preferred azoic chromophore, it will be readily appreciated by those in the art that other chromophores may be utilized. Fcr instance, Example 25 hereinabove relates to an anthraquinone chromophore. Clear- ¦
ly, any of the other chromophores described hereinabove, or described in the references mentioned hereinabove, could be substituted for the chromophores disclosed herein in connection with the xylylene diphosphonic acid dyestuffs.
1.
.

.~

-1~09V0$4~

10 g of Procion Red NX2B (CI Reactive Red 1) were dissolved in 200-250 ml of water. One gram of m-aminoben~ene phosphonic acid was dissolved in 50 ml vf water, using a small amount of caustic to aid solubilization. Then the ~ -phosphonic acid solution was slowly added to the dye solution with stirring. The initial pH of the dye solution was 6.5, and this pH fell to 5.5 during the addition of the phosphonic acid. The pH was adjusted to 6.8 with 50% caustic, and then the solution was warmed on a hot plate at 140F for ~0-30 minutes.
The resulting dye solution was cooled to room temperature and 15 g of phosphoric acid and 40 g of Cyanamide 50 (50~ solution of cyanamide) were added, and the resulting solution was diluted to a total volume of 500 ml. The pH ~ -of the final solution was 1.7.
The dye solution was then padded on 100% cotton fabric at a pickup of 70~. The padded fabric was dried for two minutes at 220F and cured for 45 seconds at 390F in a Benz unit. The fabric was-scoured with a nonionic detergent and soda ash, and then subjected to ive home la~nderings.
he retention of color on the fabric was very good.
It is ~elieved that the reaction between the ilive Red 1 dyestuff and the phosphonic ac~d was as follows:
., .

~ - 35 -:: - .... . ~ . :

` ~IV~0059~
-- : .

~ ~ .
S03Na H 11 3 --N = N~ ~ N~ + ~ N H~ A

'' NaO3S S03Na NH

, ' PO H

~03Na [~N~s~3Po3~2 Nao3s 03Na , .

, :, :

3V05~

EX~PLE 37 A reduced dye solution was prepared of a convention-al monophosphate vat dye. A solution containing 5 grams per liter of the vat dye of the ~ollowing formula:

- ``C~-O-~q o~

NH '~) f~fC;~
~, was reduced ~y the addition of 2 grams per liter of sodium hydrosulphite and, after the completion of the sodium hydro-~ulphite addition, 2 grams per liter of sodium hydroxide.
m e addition of the sodium hydroxide was accompanied by a color change, which would be expected for vat dyes, as denoting reduction of the dye to its soluble leuco form.
Five grams per liter of a wetting agent ("Igepal C0-710*"), obtained from GAF) was also added to the solution. `
Immediately after preparation of the above reduced dye solution, a sample was padded onto 100~ cotton, 3 ounce per yard sheeting, at a wet pickup of 75%. After padding, the sample was dried for 45 seconds at 220F.
A portion of the fabric sam~le was rinsed in hot water (at approximately 180F) containing 10 grams per liter of a scouring agent (Synthrapol ~SP obtained from ICI).
A portion of the rinsed sample was then washed five times according to AATCC test method 130-1970 II. The results are reported in Table 1 hereinbelow.

*Trademark of GAF Corporation for nonylphenoxypoly(ethyleneoxy) ethanol; it is a nonionic surfactant.

' .
.. . . . . . .. .

90C~S~

_ Example 37 was repeated, up through the padding ofthe cotton sheeting with the reduced dye solution. The sample was then padded a second time through a 5 gram per liter solution each of acetic acid and hydrogen peroxide.
~fter the second padding step, the sample was dried for 45 - seconds at 220F. After this oxidizing step, the sample exhibited a color change, indicating that oxidation had occurred.
Portions of the sample were rinsed and washed by the procedure of Example 37, with the results reported at Table 1 below.
-~ EX~IPLE 39 ; Example 37 was repeated, through the drying step of the padded cotton sheeting. After the drying step, the sample was padded through an aqueous solution containing ; 80 grams per liter of cyanamide and 10 grams per liter of phosphoric acid. The sample was then dried for 90 seconds at 390F. This curing step allowed the reaction of the dye, the cyanamide and the cellulose to occur.
This sample was treated with the rinsing and washing treatment described in Example 37. The results are reported in Table 1 below.

Example 38 was repeated, but after the two paddin~
steps and th~ drying step, the sample was padded through the cyanamide-phosphoric acid solution described in Example 39, and then cured at 390F for 90 seconds.
This sample was rinsed and washed by the procedure of Example 37, and test results are reported in Table 1 hereinbelow.

~, . : ; . , : . , .
. .. , : ~ . . .. .

l~9V05~1L

Example ~ Color After Rinse % Color Aftex 5 Washes 37 Pad 80.1 7.6 38 Pad ox. 40.6 10.7 39 Pad/pad 99.4 64.2 40 Pad/oxid/pad 99.2 73.5 As shown in Ta~l~e l, there was some loss of color upon rinsing but the color loss was negligible for the samples of Examples 39 and 40. Washing resulted in even more dramatic differences between Examples 37 and 38, on the one hand, and 39 and 40, on the other. A definite difference in depth of shade of the samples was readily apparent. The samples of Examples 37 and 38 showed almost complete loss of color. The samples of Examples 39 and 40, however, showed much less additional color loss after washing than the samples from experiments which did not utilize the cyanamide treatment. There was no substantial increase in color yield of the sample of Ex~mple 40 over the sample of Example 39, indicating that the chemical oxidation step had little positive effect on increasing the retention of the dye in the cellulose, with the oxidation resulting in about a 9% increase in color retention.
Examples 37-40 indicate that the aftertreatment of a dyed fabric with cyanamide, accompanied by a curing step, results in a more stable bond formation, and therefore a high-er degree of fixation and dye retention in the fiber. The normal forces involved with vat dyes, including hydrogen bonding, van der Waals and other substantive-type bonds, were insufficient to retain suitable amounts of the dye in the fiber. In distinct contrast, the reaction between the dye, the cyanamide and the cellulose created a bond which was ~sufficiently strong to exhibit good dye retention.

::, ~10S~(~05~
, . , ~ .

.
Example 37 was repeated, using a corresponding amount of a monophosphonate dye of the following formula:

'. ~,,~
~0 ~,,~ ., .

! ~, ' ' ' ' : ' , .';" ' ' " ~ ' '': ' ', '' ,' ' ' ' ' ~ ' , ",.

-- ~OYV054 The results of evaluation of treated samples of this example are set forth in Table 2.

Example 38 was repeated, but using the monophosphonate dye of Example 41. The results of testing are set forth in Table 2 below.
EXAMP~E 43 Example 39 was repeated, but using the monophosphonate dye of Example 41. The results of testing are set forth in lO~r Table 2 below.
~` EXAMPLE 44 Example 40 was repeated, but using the monophosphonate dye of Example 41. The results of color retention testing are ; reported in Table 2 below.

Example % Color After Rinse % Color After 5~fiWashes 41 38.8* 9.6*
42 64.5 13 6 - 43 89.2 64 0 44 95.2 71 8 *Average of two samples The dyes used in Example 37 and in Example 41 were identical, except the phosphate group was repl~ced with the phosphonate group. The monophosphonate dye behaved in a similar manner to the monophosphate dye, with results almost identical. The i results lead to basically the same conclusions as for Table l, and also lead to the conclusion that the phosphate and phosphonate dyes behave in a similar manner in their reaction with cyanamide and cotton.

' . ,' ~ . ' : . ' .
, ' ' ' ~ ' ' ~ , .

- l~g~

EXAMPLES 45- ~8 Examples 37 - 40 Were repeatedl but using a monophosphate vat dye of Example 13 of U. S. patent 3r3397999 which had the following formula:
OC,.- ~ \NH O

~ ~ HO- P -OH ~

Examples 45 - 48 had experimental results similar to Examples 37 - 40.
ExAMæLEs 49 - 52 Examples 37 - 40 were repeated, but using a diphos-phate vat dye of Example 2 of U . S . patent 3,339,999, having the following formula:

~\
~ ~ '~

O ~-O- ~ ~ O ~ ~ ~-P=O

' :'.
.

- 42 - :

, ~ , ,: . ~ . . . :
' ~, , , ~ : , 3~09~S~

The results obtained for these examples were similar to the results obtained for Examples 37-~0.

:
Examples 37-40 were repeated, but using a diphosphate vat dye disclosed in Example 51 of U.S. Patent 3,339,999, and having the following formula:

L0 ~ ~

O ~ C~ O ~ C ~ ~ p /

The experimental results on dyed samples of these examples were similar to the results obtained for Examples 37-40. ::

These examples relate to dyeings using a phosphate-containing dye which is not a vat~dye, and therefore the necessity for having a reduction step is eliminated. The dyestuff used in these examples had the following structure:

O,i C H H

H3C N o po3s~so3P~

O - P- OH
~H .

- ~3 - -.. . . . . .
,. ~ . :. . . . ~ .
, j . . . .

~9~05~

An aqueous pad dye bath solution was made, contain-ing 0.5 weight percent of the above dye, 0.1 weight percent of wetting agent ("Igepal CO-710"),1.0% of phosphoric acidl and 7% by weight of cyanamide, with all percentages based on the weight of the solution. Cotton samples were padded with the dye bath solution, using, in the case of Example 57, the dye bath solution described hereinabove, and, in the case of Example 58, the same solution but with the cyanamide and the phosphoric acid omitted.
The dyed samples of Example 57 (those containing the cyanamide and the phosphoric acid) had 73.7% color retention after rinsing, and 50.8% color retention after five washes, using the procedure of Example 37. On the other hand, ~xample 58, which used no cyanamide, showed practically no fixation (less than 10%).

Examples 57 - 58 were repeated, but using the phosphate-containing dye (which was not a vat dye) of the formula~

.

.' ' 10900S~
.

o_ p-OH
0~

The cyanamide dye bath solution contained only 5~ by weight of cyanamide, based on the weigh~ of the solution Example 59, which used the 5~ by weight of cyanamide, and the phos-phoric acid, resulted in 44.4% color retention after rinsing, and 39.3% color retention after five washes. On the othex hand, Example 60, which corresponded to Example ~8 in that it had no cyanamide or phosphoric acid, resulted in little or no dye fixation.
It will be appreciated from Examples 37-56 herein-above that a practical method has been developed for the application of phosphate vat dyes to cotton and cotton-containing fabrics, with good color fixation. The prior art to date was unable to use such vat dyes commercially on cotton, because of the problem of insufficient washfastness.

Using the dye of Example 24, an aqueous dye bath solution was prepared, having 0.25 weight percent of the above dye, 2 weight percent of dicyandiamide, 0.1 weight percent of surfactant ~Igepal CO 710) and 0.125 weight percent of phosphoric acid. A 100% cotton fabric was padded with this solution, passed through an oven at 400F with an -exposure time of 90 seconds, and then scoured using the pro-cedure of Example 37 and measured colorimetrically for dye retention. About 78% of the original color was retained after scouring.
i~

; ' ' ' . ~ :'; :
. - , ,. ' : . ~

~9~s~ ~ ~

EXA~PLE 62 Example 61 was repeated, except that the dye bath contained 8 weight percent, based on the weight of the bath, of a 50~ aqueous solution of cyanamide in addition to the 2 weight percent of dicyandiamide. About 87% color retention was obtained.

Example 61 was repeated, except the dicyandi~nide was eliminated from the dyebath (that is, no dicyandiamide or cyanamide was in the dyebath). The color retention after scouring was about 10%, and even more color was removed upon laundering.

:: .
A printing paste was prepared using 0.15 weight percent of the dye of Example 25, and 0.05 weight percent of the red dyestuff of the following formula:

~ C-C~ ' I ~ .

H0.35~So~Po(oy~
as well as 0.2 weight percent of wetting agent ("Igepal CO 710*") (nonylphenoxypoly(ethyleneoxy)ethanol having 10-11 ethyleneoxy units sold by GAF), 0.1 weight percent of (NH4)2HPO4, 3.0 weight percent of dicyandiamide, 33 weight percent of 3%
"Keltex S*" (aqueous solution of sodium alginate, from Kelco Company), 33.0 weight percent of a 70% "Varsol*~" emulsion, and ¦
the remainder water.
*Tradèmark **Trademark of Exxon Corporation for straight petroleum aliphatic . .

o~o~s~

The resulting print paste, with pH adjusted to 8.6, was screen printed on 100% cotton fabric at an add-on of about 5 grams per square yard (about a 100~ average add-on).
The fabric was drled and fixed at 400 F, at an exposure time of 60 seconds, to produce a printed cotton fabric having good color retention.

, Another printing paste was prepared, based on 0.2 weight percent of the blue dye of Example 25, 0.05 weight percent of the red dye having a structure as shown in Example 64, 0.2 weight percent of wetting agent ("Igepal CO 710"), 3.0 weight percent of dicyandiamide, 48 weight percent of 3 "Superloid*" (ammonium alginate sold by Kelco Company), 15.0 weight percent of a 70% "Varsol" emulsion, 2 weight percent of 50~ "Carbowax**" 4000 emulsion, and the rest water. The printing~
paste had a pH of about 4.2. The paste was screen printed using the procedure of Example 41 with similar results.
As mentioned hereinabove, it is, in some instances, desirable to add an acid to the dyebath in order to adjust the pH to the desired level. Phosphoric acid is a convenient strong acid which is preferred for such pH adjustment.
However, oth~r compounds can be used, including methyl acid phosphate, ammonium phosphate, boric acid, formic acid, lactic acid, glycolic acid and sulfuric acid.

*Trademark **Trademark. Carbowax is the trademark for the family of water-soluble polyethylene glycols and their derivatives made by the Chemicals and Plastics Division of Union Carbide Corporation.
The number following the name denotes the average molecular weight and thus the ethyleneoxy content.
"Carbowax" 4000 is polyethylene glycol; it is in the form of a white, free~flowing powder or creamy white flakes.

~..~

:~ ' . ' ' `" l~900S~

It is preferred that the dye bath contain no sol~ent or dye assistant, but in certain instances the use of such auxiliary chemicals may be useful. If an organic solvent is used to assist in bringing the reactants of the present -invention together at the reaction temperature (that is, the dye, the cyanamide compound, and the substrate), such a solvent should contain no free alcoholic-type hydroxyl group, should have a boiling polnt higher than that of water, and preferably should be miscible with water and the cyanamide compound. In such instances, suitable solvents might be "Carbowax*" 350, "Carbowax*" 750, "Carbowax*" 2000, triethylene glycol diacetate, diethylene glycol diacetate or urea. -While a wide variety of chromophores may be used in the practice of the present invention, it is generally pre-ferred that small dye molecules, compatible with color strength, be used. In general, long, linear dye molecules tend to position themselves along the cellulose polymer in such a manner that unreacted dye may be subjected to a slow release during subsequent washings, and not removed in adequate amounts during the production rinse.
Particularly preferred dyeing conditions for monophosphonic acid dyes include the use of about 0.2 weight percent surfactant, 0.2 weight percent phosphoric acid, no organlc solvent dyeing assistant, 4.0% cyanamide and 3.0%
dicyandiamide. Such a dyebath, with proper amounts of dyestuff therein, can be padded onto 100~ cotton at about 75~ pickup, and fixed at a temperature of about 390F for about 90 seconds in a Benz unit. The color endurance of the dyed fabric runs about 75-90%, with less than 5% strength loss in the fabric tear strength and warp and fill tensile strengths.
;*"CarbowaX" 350, 750 and 2000 are methoxy polyethylene glycols.

.: ' 1090~DS4 :

The process of the present invention for the continuous dye~ng of cotton equzlls or exceeds other reactive dyeing systems now in use. The present process involves a pad-predry-bake-rinse-drv system which can be utiLized on existing plant equipment. Most reactive dyeing systems are based upon alkaline dyeing environments, whereas the present system operates extremely well on the acid side with a pH of about 5, and thus is more compatible with the disperse dyes -~
used in the thermosol dyeing of polyester-cotton fabrics.
Dye migration problems can be controlled by normal adjust- -ments in the padding and predrying steps in the operating plant, and such adjustments are even easier on polyester-cotton blends~ The dyeings are quite consistently level.
The strength loss of the cotton fabric is generally under 5%, which is about normal for reactive dyeing processing steps.
The dyebaths of the present invention do not exhibit tailing (color strength loss) or ageing problems over a two-day period. ~ -As mentioned above, the monophosphonic acid dyes -used in the process of the present invention produce dyed fabrics having 70-90~ especially 75-90~, color endurance.
This color endurance can be defined as the percent color retained, compared to initial unrinsed fabric, after a full rinsing and five standard AATCC machine launderings. In ontrast, the color endurance for competitive reactive dyes a~erages about 60-70~.

_ 49 _ ;
~. .

~03~0S~
.. . .

Previous attempts by the art to develop an acid-side reactive dye system have been characterized by pOO resistance to acid perspiration, whereas the fabrics dyed according to the present process showed little or no change in color, and little or no staining of a multifibered test fabric when tested according to AATCC Test Method 15-1975~ In laundering, color loss resistance is excellent, with the results from 10-25 washes looking very favorable. The light fastness of the dyed fabrics of the present invention is at least compe-titive to other reactive dyes based on similar chromophores, and the same is true of similar tests, such as dry cleaning.
Another ma~lor advantage of the dye system of the present invention is that the present dyes are not subject to hydrolysis during storage, in distinct contrast to the reactive dyestuffs which are now on the market, which ha~e a restricted shelf life. The dyes of the present invention should last indefinitely under storage conditions, and this is basically because the present dyestuffs are stable to moisture attack, as compared to the commercially available reactive dyestuffs.
In other words, the dyes of the present invention are, in their original, unreacted state, simple acid dyes which are chemically unaffected by moisture or water in any form. Thus, they will last with full efficiency for years, and this is in distinct contrast to reactive dyestuffs designed for alkaline-side dyeings.

Another major advantaqe of the dye systems of the present invention is the high percent fixation of the dye on the fiber which can be obtained. Normally, the alkaline-side reactive dyes have about 70% fixation or so, while fixations as high as 85% can be readily obtainable with the process of the present invention.
It is to be understood that only preferred embodi-ments of the invention have been described and that numerous alternatives, substitutions and modifications are all permissible without departing from the spirit or scope of the invention as defined in the following claims: -!
".,~

'' ' '' ' .

,,,:

~900S9l SUPPLEMENTARY DISCLOSURE
In Example 64 (page 46) of the Principal Disclosure herein there is disclosed a novel :red dyestuff having the following structural formula O
H C-C-N OH
~ =N

HO3S 03H po(OH)2 ' chemically named l-hydroxy-3,6-disulfo-8-acetamido-2-(3'-phosphonophenylazo)naphthalene.
The inventive embodiment there disclosed, it has been found, embraces, in addition to the above-depicted compound ;~
the alkali metal and ammonium salts thereof. These novel bright red azo dyes exhibit properties improved over known materials, i.e., good lightfastness and color strength; they are convenient to use in commercial dyeing operations, reasonably soluble in aqueous solutions (with or without surface active agents, organic solvents or the like) and convenient to synthesize.
We have found, for instance, that these novel dyes are lightfast and are more efficient than other commonly used materials. As an example, where one pound of the novel dye compound is required to dye a given quantity of -substrate (such as 100% cotton or another fiber~ a greater amount, up to about 1.65 pounds, of another higher molecular weight dye is required to dye the same quantity of material.

.

. ~ .

, 5~

The above-recited dyes, whi:le useful as general dye-stuff materials, are particularly suitable for reactive dyeing, that is in a process where the dye is reactively linked to cellulose fibers of the substrate to be dyed by means of a phosphorus ester link produced in the presence of a carbodlimide such as cyanamide. This procedure is described in detail in our German Offen. Publication No.
2,505,497 of August 14, 1975.
Although formulated herein in its free-acid form, the acid dye of the invention may also be made and used in its alkali metal or ammonium salt forms. It preferably is used in free-acid form, more preferably in the ammonium or an acid ammonium salt form. Salts of the dye with amines which are volatile under cure conditions may also be used. The ammonium and acid ammonium salts are conveniently made by adding ammonium hydroxide to solutions of the free-acid dye.
Correspondingly, upward adjustments of pH in the dyebath are preferably made with ammonia, less preferably with a volatile amine such as dimethylamine. Downward adjustments of pH, if needed, preferably are made with hydrochloric acid or other acid volatile under curing conditions.
When used at low pH, as exemplified hereinafter, the novel free-acid dye of the invention is used in aqueous solution. At higher pH, the nature of the ammonium or alkali metal salt of the dye in solution will depend upon the ammonia or alkali metal content of the solution as measured by the pH. The ammonium salts are usually the tri--or tetra-ammonium salts, or mixtures thereof, within the general pH range employed. Mixtures of ammonium and alkali metal salts may also be used.

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.. . .

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Compounds of our invention are produced by reacting N-acetyl H-acid with diazotized m-aminobenzene-phosphonlc acid in the presence of suitable adjuncts. The preparation of N-acetyl H-acid is described in Fierz-David, "Fundamental Processes of Dye Chemistry", Interscience Publishers, 1949, at pp. 263-264. The general reaction of certain naphthol sulfonic acids with 3-aminobenzenephosphonic acid is described in Example 1 of U. S. Patent No. 3,202,550 to Grossmann et al.

H acid (Eastman produced purified by reprecipitation, 175 g. 0.5 mold), sodium carbonate (30 g), and water (750 ml) were mixed and heated to 50C to dissolve. Acetic anhydride (85 g, 0.83 mole) was added dropwise over 15 minutes and the solution then stirred for 1 hour at 50C. Sodium carbonate (75 g) was then added and the solution heated for 1 hour at 95C to reverse any acylation of the hydroxyl group. The solution was then cooled in ice.
m-Aminophenylphosphonic acid (86.5 g, 0.5 moles) and sodium carbonate (53 g, 0.5 mole) were dissolved in water (500 ml). Sodium nitrite (37 g. 0.54 mole) in water (100 ml) was added, and the solution cooled to 10C. The solution was added to concentrated hydrochloric acid (125 ml) and ice (500 g.). I'he solution was added all at once to the solution of acetyl H acid, and the solution stirred for 1 hour. Concentrated hydrochloric acid (500 ml) was then added (pH = 0.5) and the solution filtered. The precipitate~
solid was washed with glacial acetic acid and dri~d under vacuum at 50C.
Further purification to the free acid was efected by dissolving the dye in aqueous methanol and passing the ~1 ... . . .
~ '' ' ' . . . ..

1~V9(~0S~

solution through an acid ion exchange resin. Removal of the solvent yielded a dye which was, by titration, a te~rabasic acid of greater than 95% purity, thus confirming the structure illustrated above.
As a further means of analysis, the free acid was reacted in solution to make the txi-potassium salt and the solution evaporated to dryness giving the heptahydrated potassium salt having the empirical formula:

Cl 8H1 3llN3 S 2PK3 7H2 Results of elemental analysis are:

.
Theory: C 27.5 N 5.4 S 8.1 P 3.9 H2O 16.0 Molecular Weight 785 Found: C 26.9 N 5.8 S 7.7 P 3.5 H2O 15.5 Molecular Weight 789 A printing paste was prepared using 0.05 weight percent of the dye of the formula:

0 1~ .
~3C-C-N qH ~

NO35 503H PO(OH)2 and 0~15 weight percent of a blue dye of the structure:

`:;` ~09(905~

~ ~P O ( OH ) 2 CHzPO(OH)2 This dye is prepared by reacting bromaminic acid with o-amino p-xylylenediphosphonic acid as described in Example 25 of our German Offen. P 25 05 497.1.
The print paste also included 0.2 weight percent of a ~! 11 wetting agent (IgepalC0-710'7*nonylphenoxypoly(ethyleneoxy)-ethanol having 10-11 ethyleneoxy units, sold by GAF), 0.1 weight percent (NH4)2HPO4, 3.0 weight percent of dicyan-diamide, 1.0 weight percent of sodium alginate, 33.0 weight percent of 70% Varsol emulsion and the remainder water. The resulting print paste was adjusted to a pH of 8.6 with ~ ' ammonium hydroxide.
The print paste so prepared was screen printed on 100% cotton fabric at an add-on of about 5 grams per square yard (about a 100~ average add-on). The fabric was dried and fixed at 400F, at an exposure time of 60 seconds, to produce a printed cotton fabric having a good color fixation.
(This example corresponds in substance to Example 64 of the Principal Disclosure.) In the following Examples 68-70, all percentages are expressed on the weight of the bath.

*Trademark ~0900S~

. . .
A dye bath containing the following ingredients was prepared:

.. . .
L.~% Red dye of Example 66 3.0% H3PO4 (85%) 8.0% "Cyanamide AC-50" (50~) 2.0% "Carbowax 350"
0.25% "Igepal CO-710"
pH 1.5 The above bath was padded on 100% cotton at 70~ pick-up, dried at 220F, and cured for 60 seconds at 390F. The cloth was rinsed; practically no color was remo~ed.
~ EXAMPLE 69 A bath containing the following ingredients was prepared:

0.5% Red dye of Example 56 5.0% "Cyanamide AC-50 (50%) 0.5% "Igepal CO-710"
0.3% H3PO4 (~5%) pH Ad]usted to 5 with NH40H

Th~s bath was padded on 100% cotton, steamed for 1 minute at 220F and then cured 45 seconds at 390F. When the cloth was scoured with 1.7 g/l soda ash and 1.5 g/l "Synthrapol SP
at the boil for 2 minutes, a fixation of 80% was obtained.
Fixation is defined herein as that percentage of the color retained on the cloth after scouring, based on the color as it comes from the curing oven, both color measurements being taken on a Beckman DBG Spectrophotometer.

'~, .

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~he following bath was prepared:

-2.0% Red dye of Example 66 - -

4.0~ Dicyandiamide 0~1% "Igepal CO-710"
0.125~ H3Po4 (85~) pH 5 10 This bath was padded on a 50/50 blend of polyester (T54)/ cotton at 60~ pick-up, infrared pre-dried and cured 75 seconds at 400F. After scouring as in Example 69, color fixation was 70~.
As noted above, the novel dyes of the invention are usually efficient, by which it is meant that the color yield per unit of dye weight is exceptional for a dye which is wash-fast on cellulosic fabrics and yarns. The exceptional efficiency stems from the fact that the dyes give inherently intense bright red dyeings, coupled with the fact that their molecular weights are very low by comparison with the large-molecule direct dyes which are substantive to cellulosics. Hence each molecule, which is to say, each low molecular weight of it, provides a high yield of color on a pound-for-pound basis.
The low molecular weight, or expressed otherwise, the general simplicity and smallness of the moleculel provide yet another advantage to the dyes of the invention. Especially when a dye is permanently fixed to a substrate by chemical reaction, it is highly desirable that any of the dye which has failed to become reactively bound should be readily washed away during process rinsing, to provide , ..... ;

~90~S~

easy washoff, and reduce subsequent "washdown" during use.
In the dyes of the invention, the same phosphonic acid group which provides a site for reaction also serves as a strong water-solubilizing group for aiding removal of any dye molecules which are not fixed, thereby insuring efficient removal of unfixed dye during process rinsing, and reducing or even eliminating subsequent drawn-out washdown during customer use. The red dyes of the invention are believed to be easier to wash off in process rinsing than any red dye being used in commercial continuous dyeing today.
The acetyl group is provided in the dyes as the smallest group capable of overcoming the inherent susceptibility to light of H-acid dyes. Other groups will furnish lightfastness properties, but no other so efficiently as the acetyl. In other words, the acetyl group supplies lightfastness in conjunction with minimum effect on the high redness per pound of the dyes of the invention.
The dyes of the invention have a distinct advantage, compared to conventional reactive dyes which are applied under strongly alkaline conditions, that they mostly are applied under acidic conditions and thus may be applied together with disperse dyes in the same dyebath. Alkaline conditions lead to flocculation of the majority of disperse dyes, which fact drastically limits the possibilities for simultaneous dyeings of poly~ster and cotton with disperse and conventional reactive dyes. In contrast, the acid fi~ing conditions used with the phosphonic dyes of the invention have no adverse effect on disperse dyes, and the two types of dyes can be used together without difficulty.

C

", .. ' . . ' , ., , . : ... .

Claims (25)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A method of forming a reactively dyed polymeric substrate, said method comprising:
(a) contacting a polymeric substrate containing active hydrogen atoms present in the form of amino or thiol groups with a cyanamide compound selected from the group consisting of cyanamide, alkyl-substituted cyanamide, dicyandiamide, and alkyl-substituted dicyandiamide, wherein the alkyl groups each contain 1-6 carbon atoms, and with a coloring amount of a chromophore-substituted phosphorus acid of the formula:

wherein each R is a chromophore, m is 0, 1 or 2;
n is 0 or 1; p is 1 or 2; and q is 0 or 1; and m + p + q = 3, at least one of _ and q being other than 0, at a pH of from about 1.5 to about 9, wherein the equivalent ratio of said cyanamide compound to each phos-phorus acid function of said chromophore-substituted phos-phorus acid is at least about 2:1, and (b) heating the contacted substrate to a temperature of at least 200°F for a time sufficient to fix said chromophore to said substrate.

2. The method of Claim 1, wherein m is 1, n is 1, p is 2 and q is 0.

3. A method according to Claim 2, wherein said chromophore is an azo chromophore.

4. A method according to Claim 2, wherein said chromophore is an anthraquinone chromophore.

5. A method according to Claim 2, wherein said chromophore is substituted with two phosphonate radicals.

6. A method according to Claim 5, wherein said substrate is contacted with said cyanamide compound and said chromophore-substituted phosphonic acid in the absence of phosphoric acid.

7. A method according to Claim 5, wherein the phosphonate groups are on the same aromatic ring of the chromophore group.

8. A method according to claim 1, wherein said substrate is a textile substrate.

9. A method according to Claim 1, wherein said cyanamide compound is cyanamide.

10. A method according to Claim 1, wherein said cyanamide compound is dicyandiamide.

11. A method according to Claim 1, in which the pH
of the solution is adjusted to below about 3 by adding up to 5% by weight of an acid to the solution.

12. A method according to Claim 1, in which the pH of the solution is above about 2 and the chromophore-substituted acid is in the form of a fugitive amine or ammonium salt thereof.

13. A method according to Claim 1, in which the chromophore is selected from anthraquinone, phthalocyanine, azo, benzanthrone, pyrazolone, naphthoquinone, triarylmethane and cyanine.

14. A reactively dyed organic polymeric substrate of the formula where each R is a chromophore, said chromophore being linked chemically to the P atom; R1 is the chain of a polymer having reactive groups with active hydrogen atoms selected from amino groups and trio groups; m is 0, 1 or 2; n is 0 or 1; q is 0 or 1 and z is 0 or 1, and m + q + z = 3, at least one of m and q being other than 0.

15. A reactively dyed substrate according to Claim 14 wherein R1 is the residue of a polyamide chain.

16. A reactively dyed substrate according to Claim 14 wherein the polymer of which R1 is a chain thereof is a proteinaceous material selected from silk and wool.

17. A dyed substrate according to Claim 14 in which m is 1, n is 1, z is 1 and q is 0 and the chromophore is selected from anthraquinone, phthalocyanine, azo, benzanthrone, pyrazolone, naphthoquinone, triarylmethane and cyanine.

18. A method of forming a reactively dyed organic polymeric substrate comprising the steps of:
(a) contacting a polymeric substrate having reactive groups with active hydrogen atoms selected from amino groups and thio groups in the presence of a carbodiimide with a chromophore substituted phosphorus acid of the formula where each R is a chromophore, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, and q is 0 or 1, and m + p + q = 3, at least one of m and q being other than 0; and (b) heating the contacted substrate to a temperature and for a time sufficient to form a dyed substrate.

19. A method according to Claim 18,wherein the polymeric substrate is nylon.

20. A method according to Claim 18 wherein the polymeric substrate is wool.

21. A method according to Claim 18 wherein the polymeric substrate is silk.

22. A method of forming a reactively dyed organic polymer substrate having reactive groups with active hydrogen atoms selected from amino groups and thio groups comprising the steps of:

(a) contacting said substrate with a cyanamide compound of the general formula wherein X1 and X2 are each a lower alkyl group, or taken together, are wherein each X3 is a lower alkyl group, and with a chromo-phore substituted phosphorus acid of the formula:

where each R is a chromophore, m is 0, 1 or 2, n is 0 or 1, p is 1 or 2, and q is 0 or l; and m + p + q = 3, at least one of m and q being other than 0;and (b) heating the contacted substrate to a tem-perature and for a time sufficient to form a dyed substrate.

23. A method according to Claim 22 wherein the cyanamide compound is dimethylcyanamide.

24. A method according to Claim 1 wherein the contacted substrate of step (a) is dried prior to heating in step (b).

25. A method according to Claim 18 wherein the contacted substrate of step (a) is dried prior to heating in step (b).