US3478376A

US3478376A - Dyeing and printing synthetic polyamide fibres

Info

Publication number: US3478376A
Application number: US585294A
Authority: US
Inventors: Manfred Daeuble; Klaus Dieck; Hans Heinrich; Guenter Witsch
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1965-10-16
Filing date: 1966-10-10
Publication date: 1969-11-18
Anticipated expiration: 1986-11-18
Also published as: DE1469646A1

Description

United States Patent US. Cl. 8169 9 Claims ABSTRACT OF THE DISCLOSURE Process and composition for dyeing or printing polyamide fibers in which an aqueous solution of an (a) anionic dye is employed which further contains as essential assistants a mixture of (b) at least one water-soluble salt of sulfonic acids or sulfuric acid hemi-esters having a hydrophobic portion in the molecule, (c) at least one oxypropylated or oxybutylated alkylphenol or aliphatic alcohol which may also be oxyethylated, and (d) at least one monophenyl or mononaphthyl ether of ethylene glycol or diethylene glycol. The invention is useful in providing an improvement in dyed or printed fibers of synthetic polyamides having a level dyeing.

The present invention relates to a process for dyeing and printing synthetic polyamide fibers with anionic dyes and to the synthetic polyamide fibers dyed or printed according to this process. The invention also relates to a new assistant for carrying out the dyeing and printing of synthetic polyamide fibers with anionic dyes.

It is known that synthetic polyamide fibrous material can be dyed or printed by applying an aqueous solution of an anionic dye to material containing these fibers at a temperature which is lower than the temperature at which the dyes are absorbed, and then finishing off the dyeing or print by steaming. This method has serious disadvantages; for example it gives non-level dyeings.

It has therefore already been proposed to add other assistants to the dye solutions. In one prior art method of this type, condensation products of high molecular weight fatty acids with two equivalents of an alkanolamine, anion-active dispersants andif desired swelling agents for the fibers to be dyed are added as assistants to the dye solution. In another prior art method a soluble salt of a saturated aliphatic high molecular weight monocarboxylic acid is added to the dye solution. When used for dyeing synthetic polyamide fibrous material, these prior art methods require fixing of the dye with steam under pressure at 130 C. to achieve satisfactory results; under these conditions the prevailing pressure is about 2 atmospheres gauge. Since pressure steaming has been satisfactorily developed only for batchwise operation and not for continuous operation, the prior art methods for continuous dyeing and printing have little suitability for dyeing and printing synthetic polyamide fibers.

It is an object of this invention to produce level dyeings and prints on synthetic polyamide fibers by impregnation or printing with anionic dyes followed by steaming.

3,478,376 Patented Nov. 18, 1969 Another object of the invention is to carry out the fixing of the dye with steam in a process of the said type at atmospheric pressure and thus provide a simple possibility for carrying out the process continuously.

These and other objects are achieved in accordance with this invention by applying to the fibers an aqueous solution which contains (a) at least one anionic dye and (b) at least one anionic assistant at a temperature which is lower than the temperature at which any of the dyes present is absorbed, and by finishing off the dyeing or print (i.e. fixing the dye) by steaming, said aqueous solution also containing (c) at least one product obtained by separately adding on (i) 2 to 15 moles of propylene oxide or butylene oxide and (ii) 0 to 10 moles of ethylene oxide to 1 .mole of an alkylphenol having six to twelve carbon atoms in the alkyl radical or of an aliphatic alcohol having one to twenty carbon atoms and (d) at least one adduct of 1 to 2 moles of ethylene oxide to 1 mole of a hydroxy compound of the benzene series or naphthalene series which may bear other nonionic radicals on the aromatic nucleus.

The anionic dyes to be used according to this invention may belong to any class of dyes, such as those of azo, anthraquinone, phthalocyanine or nitro dyes. They may be for example 1:1 or 1:2 metal complex dyes which may or may not contain sulfonic acid groups, chrome dyes (which may be used with agents supplying chromium, such as potassium dichromate, chromium fluoride or chromium acetate), or reactive dyes. Anionic dyes are defined as those dyes referred to as Acid dyes, Mordant dyes and Reactive dyes in the Color-Index (second edition 1956).

Anionic assistants are conventionally used as additives in dyeing with anionic dyes. Preferred agents of this type are for example water-soluble salts of sulfonic acids or sulfuric acid hemiesters having a hydrophobic portion in the molecule, especially their salts with alkali metals, ammonium and particularly organic bases. Examples are the water-soluble salts of sulfuric acid hemiesters of aliphatic alcohols having ten to twenty, preferably twelve to eighteen, carbon atoms, of sulfuric acid hemiesters of adducts of alkylphenols to l to 5 moles of ethylene oxide having six to twelve carbon atoms in the alkyl radical, of alkylsulfonic and alkylarylsulfonic acids having ten to twenty carbon atoms, and of N-acyltaurines having ten to twenty carbon atoms in the acyl radical. Other anion-active assistants are the water-soluble salts of aminobenzenesulfonic acids which bear hydrophobic radicals on the nitrogen atom as substituents and of sulfosuccinic alkyl esters. It has proved to be particularly advantageous to use at least 5 parts by weight of anion-active assistant (b) to 1000 parts by weight of dye liquor or print paste. In other respects it is advantageous to adapt the amount of the anion-active assistant to the amount of agent specified, under (c). If the latter is readily soluble in water or readily dispersible, a ratio by weight of agent (b) :agent c) of 0.25:1 to 05:1 is sufiicient. If very sparingly soluble and poorly dispersible agents (c) are used, however, it is advantageous to increase the said ratio, the upper limit being about 2: 1. While it is possible to use a larger amount of anionic agent, it is advisable in theinterests of economical operation not to use more than 60 parts by weight of agent (b) to 1000 parts by weight of liquor.

Starting materials for products of the type specified under (c) may be alkylphenols, preferably p-alkylphenols, which contain a linear or branched alkyl radical having six to twelve, preferably eight to ten, carbon atoms; the benzene nucleus may bear further low molecular weight alkyl radicals, such as methyl radicals, ethyl radicals or propyl radicals, but monoalkylphenol radicals are preferred. Linear and branched aliphatic alcohols containing one to twenty, preferably six to twelve, carbon atoms are also suitable as starting materials. Examples are: p-nhexylphenol, p-n-octylphenol, p-isononylphenol, o-n-decylphenol, m-n-dodecylphenol, methanol, ethanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, isooctanol, nonanols, decanols, dodecanols, hexadecanols and octadecanols. Mixtures of these starting materials, such as are obtained for example by syntheses or from natural raw materials, may also be used.

The products defined under (c) are obtainable from these star-ting materials by adding (i) 2 to 15, preferably 2 to 7, moles of propylene oxide or butylene oxide and (ii) to 10, preferably 2 to 6, moles of ethylene oxide by a conventional method to the alkylphenols or alcohols. The starting materials may therefore be reacted only with propylene oxide or with a butylene oxide, or first with propylene oxide or a butylene oxide and then with ethylene oxide, or first with ethylene oxide and then with propylene oxide or a butylene oxide. The butylene oxide may be 1,2-butylene oxide, 2,3-butylene oxide or 2,methyl-1, 2-propylene oxide. The following table contains examples of the products defined under (c); column 1 contains the alkenoxylatable starting material, column 2 indicates the number of moles and the type of alkylene oxide added on in the first stage and column 3 indicates the number of moles and the type of alkylene oxide added on in the second stage. EO ethylene oxide, PO=l,2-propylene oxide, BO=1,2-bu-tylene oxide, iBO=isobutylene oxide (2-methyl-l,2-propylene oxide):

Methanol 6.5 B0 IsobutanoL. n-HexanoL 9 E0 Do- 9 E0 Do 9 P0 p-lstlagctylphenol 6 PO The agent (c) is preferably used in an amount of to 30 parts by weight on 1000 parts by weight of dye liquor or print paste. Larger amounts may also be used but the economics of the process may suffer in consequence.

The adducts of 1 to 2 moles of ethylene oxide to 1 mole of a hydroxy compound of the benzene series or naphthalene series are monophenyl ethers or mononaphthyl ethers of ethylene glycol or of diethylene glycol. They may bear on the aromatic nucleus (as additional nonionic radicals) particularly atoms, preferably chlorine atoms, hydroxyl groups, low molecular weight aryl groups, particularly the phenyl group, alkyl groups having up to five carbon atoms and/ or alkoxy groups having up to five carbon atoms. Examples are the reaction products of 1 to 2 moles of ethylene oxide with 1 mole of hydroxybenzene, lhydroxy-2-methylbenz ene, 1-hydroxy-4-methylbenzene, 1-hydroxy-4-phenylbenzene, l-hydroxy-Z-methoxybenzene, l-hydroxynaphthalene, 2-hydroxynaphthalene, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4- dihydroxybenzene and l,S-dihydroxynaphthalene. The use of the adducts of 1 mole of ethylene oxide to l-hydroxy- 2-chlorobenzene and to l-hydroxy-4-chlorobenzene is preferred.

Component (d) may be added preferably in an amount of 5 to 40 parts by weight on 1000 parts by weight of dye liquor or print paste. Whereas below the preferred range, the effectiveness of the agent gradually decreases, it is not detrimental to use larger amounts. The limits stated are dictated by economic considerations.

The liquors may also contain other conventional additives, for example acids, such as acetic acid; swelling agents, such as benzyl alcohol; solubilizers, such as low molecular weight alcohols, glycols and butyrolactone; antifoams, such as high molecular weight aliphatic alcohols; and thickeners. It is preferred however to use liquors which do not contain thickeners or contain them only in small amounts up to about 5 parts by weight on 1000 parts of liquor. In dyeing with dyes which are capable of reacting with suitable metals to form complexes, for example the chrome dyes, the mixture of assistants may be salted out by adding agents supplying metal, for example chromium fluoride or chromium acetate, thus leading to separation into two layers and ineffectiveness of the system. This can be prevented by adding chelating agents, for example a-cyanocyclopentanone, [i-diketo compounds or B-ketoesters, such as acetylacetone, a-acetylbutyrolactone, cyclopentanone-Z- carboxylic esters or acetoacetic esters. The complex-forming metal is thus bound and losses the property of salting out the assistant system from the solution. It is not necessary to bind the metal ions completely; it is sufiicient to add about 1 mole of the chelating agent to 1 mole of the metal salt used, for example chromium fluoride. However, attention should be paid to the fact that hydrogen ions are liberated in the formation of the chelate and contribute to the acidity of the liquor. Less acid is therefore required.

The fibers to be dyed may consist of any synthetic polyamide, for example poly-epsilon-caprolactam, polyhexarnethylene adipamide, cocondensates of caprolactam, adipic acid and hexamethylene diamine, polyhexamethylene sebacamide, poly-omega-oenantholactam or polyomega-undecanoic acid. They may be present in any form, for example as flocks, tops, yarn or cloth; the advantages of the present process are particularly evident in the case of pile fabrics and tufting material. The fibrous material to be dyed may consist exclusively of synthetic polyamide fibers or may contain these together with other fibers, such as cellulose fibers, hard fibers or synthetic fibers; for example in the case of tufting carpets, the backing fabric usually consists of cheap jute fibers onto which the polyamide yarn is tufted.

Application of the dye liquor to the material to be dyed may be effected for example by printing, coating or spraying. It is preferred to use the padding method. Among printing methods, the vigoureux printing of slivers has proved to be particularly suitable.

The temperature used is lower than the absorption temperature of all the dyes present. The absorption temperature of a dye is defined as that temperature at which the dye migrates from the aqueous dye solution to the material being dyed to an appreciable extent within conventional treatment periods; more specifically, the abliquor and sorption temperature is that temperature at which half of the dye originally present in the dye solution migrates to the material being dyed within thirty minutes. It is advantageous to apply the dye liquor to the material at a temperature as much as possible below the absorption temperature of the dyes; it has been found to be particularly advantageous to use temperatures at or near to room temperature, i.e., at from about to 40 C.

The dye may be fixedin the conventional way by treatment With saturated steam at about 95 to 130 C. It is particularly advantageous to use saturated steam at 100 to 102 C. or slightly superheated steam at temperatures of up to 110 0., preferably up to 105 C. Under these conditions it is possible to use atmospheric pressure; the use of complicated pressure steamers which are often liable to develop faults is thus avoided and the process is particularly suitable for continuous operation. Steaming times of five to fifteen minutes, preferably six to ten minutes, are necessary at 100 to 110 C. depending on the depth of color.

After the dye has been fixed, the dyed material may be washed, rinsed and dried in the usual way.

The present process may be carried out batchwise or continuously.

The invention is illustrated by the following examples in which the parts specified are parts by weight.

EXAMPLE 1 20 parts of the dye having the Color Index (C.I.) No. 12,715 is made into a paste with 30 parts of the condensation product of 2 moles of ,B-naphthalenesulfonic acid and 1 mole of formaldehyde with an addition of 50 parts of water and finely ground until a stable dispersion has been obtained. This dispersion is then diluted with another 500 parts of water, and 2 parts of an adduct of 40 moles of ethylene oxide to 1 mole of castor oil, 20 parts of the triethanolamine salt of decylbenzenesulfonic acid, 20 parts of the adduct of first 2 moles of propylene oxide and then 5 moles of ethylene oxide to 1 mole of isononanol and parts of p-chlorophenyl monoglycol ether are added. The whole is made up with water to 1000 parts of padding liquor. A tufting carpet of textured nylon 6 monofilarnents tufted into a jute fabric is impregnated with this padding squeezed, and the material, while still wet with padding liquor, is steamed for ten minutes at 100 C. in a spiral steamer in an atmosphere of saturated steam.

After the carpet has been washed in hot water, a material dyed a deep bluish red shade is obtained which does not exhibit any streakiness and which has outstanding general fastness properties.

EXAMPLE 2 1 part of the finely divided dye obtained by chroming a mixture of 1 part each of the chromium-free dyes Cl. No. 12,195 and Cl. No. 12,197 is finely dispersed in 600 parts of water, and then parts of the monoethynolamine salt of dodecylbenzenesulfonic acid, 20 parts of the adduct of first 5 moles of propylene oxide and then 5 moles of the ethylene oxide to 1 mole of isodecanol and 10 parts of p-chlorophenyl monoglycol ether are added. The whole is made up with water to a total of 1000 parts of padding liquor.

A tufted carpet of textured polyamide monofilaments (nylon 6) which have been tufted into a jute fabric is impregnated with this solution, squeezed out by means of a padding machine and steamed for 'five minutes at 100 to 102 C. in an atmosphere of saturated steam. The carpet is washed and dried. A material dyed a pale grey shade is obtained which has very good levelness and penetration and very high light and wet fastness.

By using 40 parts of the dye specified in the first paragraph and also adding 5 parts of oleic acid diethanolamide, the procedure otherwise being the same, a tufted carpet dyed a fast deep black shade is obtained. In this case the steaming time is twelve minutes at 100 to 102 C.

EXAMPLE 3 30 parts of the finely divided dye C.I. No. 15,675 is dissolved in 600 parts of water and then 20 parts of the sodium salt of the sulfuric acid hemiester of oleyl alcohol, 20 parts of an adduct of first 2 moles of propylene oxide and then 5 moles of ethylene oxide to 1 mole of isononanol, 10 parts of a mixture of o-chlorophenyl and p-chlorophenyl monoglycol ether and 5 parts of glacial acetic acid are added and the whole is made up to 1000 parts with water.

Nylon 6 sliver is impregnated with this padding liquor and steamed for ten minutes at to 102 C. in an atmosphere of saturated steam. The sliver is then washed. A deep bluish red material is obtained having very good fastness properties.

The following anionic compounds may be used instead of the sulfuric acid hemiesters of oleyl alcohol:

(a) 20 parts of the sodium salt or triethanolamine salt of an adduct of 2 to 4 moles of ethylene oxide to 1 mole of nonylphenol;

(b) 20 parts of the sodium salt of Kogasin sulfonic acid;

(c) 20 parts of sodium monobenzylnaphthalenesulfonate;

(d) 25 parts of diethanolammonium diisopropylnaphthalenesulphonate;

(e) 20 parts of the sodium salt of oleic acid tauride;

(f) 20 parts of the sodium salt of isohexylisopropylnaphthalensulfonic acid.

EXAMPLE 4 15 parts of the finely divided dye C.I. No. 18,690 is dissolved in 500 parts of water and then 20 parts of the monoethanolamine salt of dodecylbenzenesulfonic acid, 20 par-ts of the adduct of 6 moles of propylene oxide to 1 mole of isooctanol, 10 parts of p-chlorophenyl monoglycol ether and 5 parts of glacial acetic acid are added. The whole is then made up to 1000 parts with water.

Knitted goods made of textured nylon 6,6 fibers, which have been crimped and elasticized by the false twist method, are impregnated with the said solution, squeezed out and steamed at 100 C. for ten minutes. The goods are then washed and dried. Knitted goods dyed a reddish yellow shade are obtained which have extremely good levelness and very good general fas-tness properties.

In the process described in Example 4, the products specified in Examples 5 to 23 may be used with the same success instead of the adduct of 6 moles of propylene oxide to 1 mole of isooctanol.

EXAMPLE 5 20 parts of the adduct of first three moles of propylene oxide and then 3 moles of ethylene oxide to 1 mole of isooctanol.

EXAMPLE 6 15 par-ts of the adduct of first 6 moles of butylene oxide and then 2 moles of ethylene oxide to 1 mole of isooctanol.

EXAMPLE 7 15 parts of the adduct of 5 moles of propylene oxide to 1 mole of isohexanol.

EXAMPLE 8 20 parts of the adduct of first 3 moles of propylene oxide and then 1 mole of ethylene oxide to 1 mole of isodecanol.

EXAMPLE 9 20 parts of the adduct of first 3 moles of propylene oxide and then 4 moles of ethylene oxide to 1 mole of isodecanol.

7 EXAMPLE 10 20 parts of the adduct of first 4 moles of propylene oxide and then moles of ethylene oxide to 1 mole of n-decanol.

EXAMPLE ll 20 parts of the adduct of first 4 moles of butylene oxide and then 5 moles of ethylene oxide to 1 mole of isononanol EXAMPLE 12 15 parts of the adduct of first 4 moles of butylene oxide and then 3.5 moles of ethylene oxide to 1 mole of isononanol EXAMPLE 13 20 parts of the adduct of first 5 moles of isobutylene oxide and then 1 mole of ethylene oxide to 1 mole of isobutanol.

EXAMPLE 14 parts of the adduct of first 3 moles of ethylene oxide and then 3 moles of propylene oxide to 1 mole of isooctanol.

EXAMPLE 15 parts of the adduct of 6 moles of propylene oxide to 1 mole of p-nonylphenol.

EXAMPLE 16 20 parts of the adduct of first 2 moles of ethylene oxide and then 3 moles of butylene oxide to 1 mole of isooctanol.

EXAMPLE 17 20 parts of the adduct of first 5 moles of ethylene oxide and then 3 moles of butylene oxide to 1 mole of isooctanol.

EXAMPLE 18 20 parts of the adduct of first 2 moles of ethylene oxide and then 3 moles of propylene oxide to 1 mole of isooctanol.

EXAMPLE 19 10 parts of the adduct of first 2 moles of propylene oxide and then 3 moles of ethylene oxide to 1 mole of isodecanol.

EXAMPLE 20 20 parts of the adduct of first 4 moles of propylene oxide and then 4 moles of ethylene oxide to 1 mole of isodecanol.

EXAMPLE 21 20 parts of the adduct of first 4 moles of propylene oxide and then 8 moles of ethylene oxide to 1 mole of ndecanol.

EXAMPLE 22 20 parts of the adduct of first 2 moles of butylene oxide and then 8 moles of ethylene oxide to 1 mole of isononanol EXAMPLE 23 20 parts of the adduct of first 4 moles of butylene oxide and then 4 moles of ethylene oxide to 1 mole of isodecanol.

EXAMPLE 24 20 parts of the dye having the Cl. No. 19,115 is dissolved in 500 parts of water and then 20' parts of the adduct of firs-t 2 moles of propylene oxide and then 5 moles of ethylene oxide to 1 mole of isononanol, 20 parts of the sodium salt of Kogasin sulfonic acid and 10 parts of p-chlorophenyl glycol ether and 15 parts of glacial acetic acid are added and the whole made up to 1000 parts with water. A carpet which has been prepared by tufting textured polyamide yarns into jute fabric is impregnated with this solution, squeezed out on a padding machine and steamed in an atmosphere of saturated S steam at to 102 C. A level bluish red dyeing having high light fastness is obtained.

We claim:

1. In a process for dyeing or printing synthetic polyamide fibers by applying thereto an aqueous solution which contains:

(a) at least one anionic dye;

(b) in 1000 parts by weight 5 to 60 parts by weight of at least one anion-active dye assistant which is a water-soluble salt of a sulfonic acid or of a sulfuric acid hemi-ester having a hydrophobic portion in the molecule, at a temperature which is lower than the absorption temperature of all dyes present and finishing off the dyeing or print by steam, the improvement which comprises employing a dye solution which also contains in 1000 parts by weight:

(c) 5 to 30 parts by weight of at least one oxyalkylated product obtained by the separate addition in any order of (i) a block of 2 to 15 moles of propylene oxide or butylene oxide and (ii) a block of 0 to 10 moles of ethylene oxide to 1 mole of an alkylphenol having six to twelve carbon atoms in the alkyl radical or of an aliphatic alcohol containing one to twenty carbon atoms; and

(d) 5 to 40 parts by Weight of at least one monophenyl ether or mononaphthyl ether of ethylene glycol or diethylene glycol which may bear on the aroma-tic nucleus a halogen atom, a hydroxyl group, a phenyl group, an alkyl group having up to five carbon atoms or an alkoxy group having up to five carbon atoms.

2. A process as claimed in claim 1 in which a watersoluble salt of a sulfuric acid hemiester of an aliphatic alcohol having ten to twenty carbon atoms, of a sulfuric acid hemiester of an adduct of an alkylphenol having six to twelve carbon atoms in the alkyl radical and one to five times the molar amount of ethylene oxide, of alkylsulfonic acids 'or alkylarylsulfonic acids having ten to twenty carbon atoms or of N-acyltaurines having ten to twenty carbon atoms in the acyl radical is used as an anion-active assistant.

3. A process as claimed in claim 1 in which ingredents (b) and (c) are used in the ratio by weight of 0.25:1 to 2:1.

4. A process as claimed in claim 1 in which p-chlorophenyl ethylene glycol ether is used as ingredient (d).

5. A process as claimed in claimed 1 in which an oxyalkylated product obtained by the separate addition in any order of (i) a block of 2 to 7 moles of propylene oxide or butylene oxide and (ii) a block of 2 to 6 moles of ethylene oxide to 1 mole of an alkylphenol having eight to ten carbon atoms in the alkyl radical is used as ingredient (c).

6. A process as claimed in claim 1 in which an oxyalkylated product obtained by the separate addition in any order of (i) a block of 2 to 7 moles of propylene oxide or butylene oxide and (ii) a block of 2 to 6 moles of ethylene oxide to 1 mole of an aliphatic alcohol having six to twelve carbon atoms is used as ingredient (c).

7. A process as claimed in claim 1 in which a dye solution is used which contains not more than 5 parts by weight of thickener in 1000 parts by weight of dye solution.

8. A composition for the dyeing or printing of synthetic polyamide fibers which comprises an aqueous solution of an anionic dye containing in 1000 parts by weight of the dye solution, in addition to (a) at least one anionic dye, a mixture of assistants which consists essentially of the following ingredients:

(b) 5 to 60 parts by weight of at least one anion-active dye assistant which is a water-soluble salt of a sulfonic acid or of a sulphuric acid hemi-ester having a hydrophobic portion in the molecule;

(0) 5 to 30 parts by weight of at least one oxyalkylated product obtained by the separate addition in any order of (i) a block of 2 to 15 moles of propylene oxide or butylene oxide and (ii) a block of 0 to 10 9 10 moles of ethylene oxide to 1 mole of an alkylphenol References Cited having six to twelve carbon atoms in the alkyl radi- UNITED STATES PATENTS cal or an allphatlc alcohol havlng one to twenty 3,377,130 4/1968 Willson et a1. v8 90 carbon atoms; and

(d) 5 to 40 parts by weight of at least one monophenyl 5 FOREIGN PATENTS ether or mononaphthyl ether of ethylene glycol or 976,529 11/ 1964 Gre t Britain. diethylene glycol which may bear on the aromatic nucleus a halogen atom, a hydroxyl group, a phenyl NORMAN TORCHIN, Primary EXaminel' group, an alkyl group having up to five carbon atoms s CALLAGHAN, Assistant Examiner or an alkoxy group having up to five carbon atoms. 10

9. Fibers of synthetic polyamides which have been U.S. Cl. X.R.

dyed or printed by the process claimed in claim l. 8-90, 93, 178