US2950949A - Process for dyeing and printing shaped structures of hydrophobic organic high polymers containing ester groups - Google Patents

Description

PROCESS FOR DYEING AND PRINTING SHAPED STRUCTURES OF HYDRQPHOBIC ORGANIC HIGH POLYMERS CONTAINING ESTER GROUPS Paul Schlack, Leitershofen, near Augsburg, Germany, assignor to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Briining, Frankfurt am Main, Germany, a corporation of Germany .No Drawing. Filed Apr. 23, 1957, Ser. No. 654,467 Claims priority, application Germany Apr. 28, 1956 8 Claims. (Cl. 8-55) The present invention relates to a process for dyeing and printing shaped structures of hydrophobic organic high polymers containing ester groups.

When operating under the conditions usually applied for the dyeing of acetate rayon or polyamide fibres the affinity to dispersion dyestuffs of the synthetic fibres, for example on the base of terephthalic acid, made of linear high-melting polyesters containing six-membered carbocyclic rings is in most cases not sufiicient, not even when operating at boiling temperature.

In order to attain a satisfactory utilization of the dyestuffs especially when deeper shades are to be obtained, dyeing has either to be carried out under pressure at temperatures considerably above 100 C. or dyeing auxiliaries, so-called carriers provoking a slight swelling of the compact fibre and thus opening it to the dyestutf molecules have to be added.

Dyeing under pressure requires expensive apparatuses. Moreover, it has to be taken into account that this process is not generally applicable. Thus, one will meet with difficulties when the textiles contain not only polyester filaments but also fibres that are very sensitive to heat. Difficulties are particularly great if the textiles contain wool, which especially when treated in a neutral bath, cannot be exposed to temperatures much above 100 C. This applies also to some synthetic fibres, for example, to fibres of polyvinyl alcohol. For the dyeing of piece-goods under pressure special devices are necessary which in practice have not yet become popular.

Numerous substances have already been proposed for dyeing with the use of carriers, most of them, however, have more or less considerable drawbacks such as for example too great a volatility, an offensive odour, physiologically disadvantageous properties, a detrimental influence on the fastness to light and difiiculties with regard to the levelling of the goods, the ditficulties being especially great when dyeing mixed fabrics. This is particularly true of mixtures of fabrics consisting of polyester material and wool.

Now I have found that shaped structures of hydrophobic organic high polymers containing ester groups, particularly of high-melting linear polyesters containing six-membered carbocyclic rings may be dyed and printed with dispersion dyestuffs if compounds that are sparingly or not at all soluble in water and contain one or more lactone groups in addition to at least one aromatic nucleus are used as auxiliaries. According to the process of the present invention there are preferably used compounds in which the lactone ring and an aromatic nucleus are joined by ortho-fusion (as the two rings in naphthalene). It proved to be suitable to select such compounds as do not contain more than two aromatic nuclei. It is furthermore of advantage to use compounds that are somewhat, even if sparingly soluble in water. As lactones coming into consideration for the process of the present invention, the following com- Patented Aug. 30, 1960' pounds, which are all 'y-lactones having S-membered lactone rings or fi-lactones having 6-membered lactone rings, may for example be mentioned:

Dilactones may also be used. By way of example there may be mentioned the compound of the following formula:

0 w (:0 LE O...

Instead of using the above compounds separately there may of course also be used mixtures of the different lactones or mixtures of lactones and other usual carriers. in conjunction with suspension dyestuffs generally used for dyeing and printing polyester goods, the lactones mentioned above may be employed for all the usual dyeing methods such as dyeing in flocks, dyeing in the rope form, dyeing in balls, piece-dyeing in the open vat, on the jig or on the dipping frame. The lactones may furthermore be applied for the pad-dyeing process and for the continuous dyeing of cables and combed material. According to a prior suggestion these dyeing processes may be combined with a stretching process by impregnating the unstretched cable of filaments continuously with a dyestutf mixture containing, apart ingly volatile with steam, will be preferred.

The amount of auxiliary agent to be used for the dyeing or printing according to the present invention depends on the etficiency i.e. on the affinity to the fibre, which atlinity may in the case of water-soluble compounds be defined by the degree of distribution betweenbath and fibre. What amount is to be used depends moreover on the depth of shade which is desired, on the goods-to-liquor ratio applied and on the speed of difliusion in the fibre. It has to be taken into account in this connection that the pretreatment of the goods, especially the thermofixation also exerts an influence on the affinity of the swelling agents to the fibre.

When compounds are used that are not or only-to a small extent soluble in water and which, as a rule, are applied together with a dispersing agent, 1-3 grams per liter .are generally sufficient. In certain cases it may even suffice to' use smaller quantities 'such ,as for example a quantity. of 0.5 gram. When operating with quantities that are a little greater than those mentioned.

In such cases a quantity of about 2-6 grams per litre is in general suflicient but there may also be used larger quantities, e.g. 8 or 10-45 grams, which does, however, in general not increase the effect considerably. The values mentioned above apply to an average goods-toliquor ratio of about 1:40.

It is not absolutely necessary that the dycstuif should be present in the bath from the beginning. The goods to be dyed may for example first be treated at an elevated temperature, at e.g. 80400 C. merely with the carrier, the dyestufif being added to the bath later on, or the material may be pretreated in a standing bath with a solution or a dispersion of the carrier in order to be subsequently dyed in a second bath to which, if necessary, a comparatively small amount of a carrier is added, which carrier need not be the same as that used in the bath of the pre-treatment.

It is merely necessary to add a lactone of the present invention to one of the baths as an auxiliary agent. It may be of advantage that thecarrier used in the dyebath proper has a greater efiiciency, i.e. a stronger aifiru'ty, and is added in a relatively smaller amount than the carrier used in the pretreatment bath. The pretreatment bath may thus contain for example a methyl phthalide or, if a lower melting point is to be obtained, a mixture of methyl phthalides whereas a lactone of the naphthalene series is added to the dyebath.

The process of the present invention admits of dyeing in a single bath mixtures of fibres made of the polyesters coming into question and wool and other protein fibres, without any difficulties occurring with regard to the shading. In order to obtain very deep shades when dyeing such mixtures of polyester fibres and wool, it is advisable to free the wool after the dyeing of the synthetic fibres, first from the adhering dispersion dye stuff by way of a dithionite bath and then to dye the wool. For this cleaning operation the usual auxiliary stripping agents may be used such as for example surface-active quaternary ammonium compounds or colloids having an aflinity to dyestuffs such as polyvinyl pyrrolidone or copolymers of vinyl pyrrolidone with other vinyl monomers such as acrylic acid.

Generally, the auxiliary agents used according to the present invention ditfer from the carrier substancesv hitherto customarily used in dispersions such as, for example, halogenated aromatic compounds or esters of aromatic carboxylic acids, by their more even effect which will especially be noticed when there is a distinct solubility in water. In the latter case the risk of stain formation is consider-ably diminished as the dyeing is brought about more gradually. Thus shading is facilitated.

A manner of proceeding according to the present invention, which is especially advantageous in the case of textile goods showing a very dense style of weaving and being diflicult to dye in a uniform manner, is to use instead of the finished lactones the hydroxyacids, on which the corresponding lactones are based, in form of their salts, and to close the lactone ring during the dyeing process by acidifying the bath or by allowing it to become gradually acid and/or by means of a rise in temperature, whereupon dyestuff and lactone are absorbed by the fibre in a uniform manner, the lactone being more or less taken up in statu nascendi. The present process is suitably carried out with hydroxyacids which are distinguished by a marked tendency to the ring closure, even in high dilution. Consequently, this modification of the process of the present inven tion is especially advantageous in the case of lactones that are sparingly soluble in water. If necessary, also in this case dyeing is carried out in the presence of dispersing agents, especially in the presence of anionic or non-ionic dispersing agents. 1

In order to liberate the hydroxyacids gradually from their salts and thus to provide the conditions under which the formation of 'lactones can take place, there may for example be applied the ammonium salts of the hydroxyacids. The alkali metal salts may also be used together with ammonium salts. As automatic acid formers, especially in conjunction with alkali metal salts, there may also be added such compounds as are hydrolyzed by water into acids especially in the heat, as for example easily hydrolizable esters, such as oxamic acid esters or tartaric acid esters, imides such as phthalimide, salts of halogen-carboxylic acids that can easily be split such as sodium chloroacetate. A gradual and cautious admixture of free acids such as formic acid, acetic acid or glycolic acid is of course also possible.

Though the proess of the present invention is preferably directed to the dyeing and printing of shaped structures made of hydrophobic organic high polymers containing ester groups, especially of shaped structures made of high-melting polyesters containing six-membered carbocyclic rings as for example the polyesters of terephthalic acid, it is as a general principle also applicable to other hydrophobic synthetic materials containing a variety of ester groups in the molecule and being difli cult to dye such as cellulose triacetate or linear polyurethanes. As shaped structures there come for example into consideration fibres, filaments, small ribbons, hanks, foils and materials made thereof such as textile fabrics.

The following examples illustrate the invention but they are not intended to limit it thereto.

Example 1 2.54 grams of the lactone of Z-hydroxy-naphthalenel-fi-propionic acid are added at a temperature of 60 C. to a dyebath containing in 875 cc. of water 2 grams of a condensation product from an alkyl phenol and ethylene oxide which condensation product was additionally esterified with sulfuric acid, 0.34 gram of the dispersion dyestuif of the formula and 1 cc. of an aqueous solution of glycolic acid of 33% strength.- 17 grams of yarn made of polyethylene glycol terephthalate (Nm 18/ 3, individual titre 3.6 deniers, staple length mm.) are introduced into the liquid which has become turbid by the dispersion of the lactone. The dyebath is slowly brought to the boil. At the boiling point the bath quickly clarifies. The dyeing is carried out for one hour at 97-98 C., during which time the bath is nearly exhausted. Subsequently the dyed material is thoroughly rinsed and washed for 20 minutes at C. in a bath containing 2 grams of soap and 1 gram of sodium carbonate per litre. A full shade of pink of a very good fastness to rubbing and washing is obtained.

Example 2 2.6 grams of 4.6-dimethyl-cumarin .dissolved in a small quantity of methanol are admixed at 60 C. to 1 litre of a dyebath containing 2 grams of a condensation product from an alkyl phenol and ethylene oxide which condensation product had additionally been esterified with sulfuric acid, 0.35 gram of the dyestufi of the formula OGHs (H) NH:

and 1 cc. of glycolic acid of 33% strength. A fine dispersion of the lactone is formed. Into the bath thus prepared there are introduced.17.3 grams of a yarn of "AL-wpolyethylene glycol terephthalate (Nm 48/2, 3.0 deniers, '100 mm.), which yarn had previously been fixed in the rope form at 110 C. The bath is gradually brought to the boil while the material to be dyed is well moved. The dyeing process is then continued for one hour at 9798 C. After a boiling time of about 20 minutes, the bath, which had turned dull milky owing to the precipitating dimethyl-cumarin, clarifies. After having been dyed the goods are thoroughly rinsed and then washed for 20 minutes at 90 C. in a bath containing 2 grams of soap and 1 gram of sodium carbonate per litre.

A brilliant deep bluish red shade of a very good fastness to washing and rubbing is obtained.

Example 3 4.5 grams of 6-methyl-phthalide are heated together with 15 cc. of a 2 N-methanolic sodium hydroxide solution 'until the lactone ring is completely opened. The solution thus obtained is then admixed at 60 C. to a dyebath containing in 900 cc. of water 4 grams of ammonium chloride, 2 grams of a condensation product from an alkyl phenol and ethylene oxide which condensation product was additionally esterified with sulfuric acid, and 0.36 gram of the dyestufi of the formula NH: ii i CONHs H A o NH-CHa Into this dyebath are introduced 18 grams of a fabric of polyethylene glycol terephthalate (3 deniers) and the bath is then slowly heated to the boiling point. After 20 minutes the pH value of the bath is adjusted to 6 by cautious addition of mineral acid. The dyeing is completed within 70 minutes at a temperature of 9798 C., the goods to be dyed being constantly moved during this time. Finally the fabric is thoroughly rinsed and then washed for 20 minutes at 90 C. in a bath containing 2 grams of soap and 1 gram of sodium carbonate per litre.

A clear deep blue shade of a very good fastness to washing and rubbing is otbained.

Example 4 4.5 grams of 4.6-dimethyl-cumarin are heated together with 15 cc. of a 2 N-methanolic sodium hydroxide solution until the lactone ring is completely opened. The solution of the sodium dimethyl-cumarate is then admixed at 60 C. to a bath containing in 900 cc. of water 4 grams of ammonium chloride, 2 grams of a condensation product from an alkyl phenol and ethylene oxide which condensation product was additionally esterified with sulfuric acid, and 0.36 gram of the dyestuff mentioned in Example 3. After having introduced 18 grams of a fabric of polyethylene glycol terephthalate into the bath the latter is slowly heated to boiling and boiled for 20 minutes. By the addition of mineral acid the pH value of the bath is then adjusted to 5-6. Further dyeing and working up are carried out as described in Example 3. In this case, too, a clear deep blue shade of a very good fastness to Washing and rubbing is obtained.

Example 5 onto GEN-ON: Q

and naphthalene sulfonic acid, and 1 cc. of glycolic acid of 33% strength. The bath remains clear. Into the dyebath thus prepared there are introduced 21.25 grams of a yarn made of polyethylene glycol terephthalate (Nm 48/2, 3 deniers, mm., fixed prior to dyeing with steam at C.). The dyebath is slowly brought to the boil. The material is dyed for 1 hour at 97-98 C. while it is constantly moved. The bath is almost completely exhausted thereby. After having been rinsed thoroughly the goods are soaped for 20 minutes as described in Examples 1-3. The dyeing obtained is fast to washing and rubbing.

Example 6 2.8 grams of the lactone of Z-hydroxynaphthalene-l-B- propionic acid dissolved in a small quantity of methanol are added while stirring to 1 litre of a bath containing 2 grams of a condensation product from an alkyl phenol and ethylene oxide which condensation product was additionally esterified with sulfuric acid, 1 cc. of glycolic acid of 33% strength and 0.425 gram of the dispersion dyestuff of the formula I l 02 i NH} Into the dull milky bath thus obtained there are then introduced 21.25 grams of a yarn made of polyethylene glycol terephthalate (Nm 48/2, 3.0 deniers, 100 mm., fixed in the dry state at C.) and the bath is slowly heatedto boiling. After a boiling time of l hour which suflices to practically exhaust the bath, the goods. are thoroughly rinsed and then washed at 90 C. as described in Examples 1-3.

The dyeing obtained has a good fastness to washing and rubbing.

Example 7 A concentrated solution of sodium dimethyl cumarate corresponding to 2.7 grams of 4.6-dimethyl-cumarin and 0.4 gram of dimethyl oxalate are added at 50 C. to a bath containing in 900 cc. of water 0.36 grain of the dyestutf of the formula ll 0 NH;

which dyestuff was dispersed in a mixture of 0.036 gram of dibutyl-naphthalene-sulfonic acid and 0.36 gram of a dispersing agent that had been obtained by condensation of cresol, formaldehyde and sodium sulfite and by subsequently heating the product obtained with fl-naphthalene sulfonic acid, formaldehyde and sodium sulfite.

After having introduced into the bath 18 grams of a fabric as has been described in Example 4 the bath is gradually heated to the boil and boiled for 10 minutes. Its pH value is then adjusted to 4.5 by means of acetic acid. The fabric is boiled for another 50 minutes and then completed in the way described in Example 3.

A very clear deep and reddish violet dyeing is obtained.

During the whole of the dyeing process the bath remains clear. There is no disadvantageous formation of foam. In order to increase the security of working there may be added a small quantity of a condensation product from naphthalene sulfonic acidand formaldehyde. Practically the same depth of shade is obtained when the sodium dimethyl cumarate is replaced by the sodium salt of cumaric acid of 4-methyl-cumarin.

7 Example 8 2.1 grams of the dilactone of the formula (IZHs I OH and 6.9 grams of phthalimide serving as acid forming agent. After having introduced 14 grams of a fabric of polyethylene terephthalate into the bath the latter is slowly heated to the boil, whereby the previously suspended phthalimide dissolves. After 1 hours dyeing at boiling temperature the goods are thoroughly rinsed. A clear yellow dyein of medium depth and of good fastness to wet processing is obtained.

Example 9 A solution of sodium cumarate obtained by heating 2.2 grams of cumarin together with 0.65 grain of sodium hydroxide in a small quantity of methanol, is admixed at 45 C. to a dyebath containing in 750 cc. of water 0.3 gram of 1,4,5,S-tetra-arnino-anthraquinone and 1.5 grams of N-dimethyl-N-fl-hydroxyethyl-N-stearoylamido propylamrnonium-hydrogenphosphate and 1.45 grams of dimethyl oxalate. After addition of 14.9 grams of a poplin fabric of polyethylene terephthalate the bath is brought to the boil. After 1 hours boiling the goods are rinsed and soaped again at 70 C. A clear deep dyeing of a good fastness to wet processing is obtained.

I claim:

1. A process for dyeing and printing shaped structures 35 of hydrophobic linear organic high polymers containing ester groups with dispersion dyestuffs which comprises dyeing said structures in the presence of an aromatic compound containing from one to two aromatic rings and substituted by from one to two lactone rings having from 5 to 6 ring members.

2. A process for dyeing and printing textile materials of hydrophobic linear high melting organic polyesters containing six-membered carbocyclic rings with dispersion dyestuffs which comprises dyeing said materials in a bath in the presence of an aromatic compound containing from one to two aromatic rings and substituted by from one to two lactone rings having from 5 to 6 ring mem: bers.

3. The process defined in claim 2 wherein the aromatic compound is a benzene having a lactone ring with from 5 to 6 ring members joined thereto by ortho-fusion.

4. The process as defined in claim 2 wherein the textile material is, before dyeing, contacted in an aqueous bath with an aromatic compound containing from one to two aromatic rings and substituted by from one to two lactone rings having from 5 to 6 ring members.

5. The process as defined in claim 2, wherein said lactone substituted aromatic compound is formed during dyeing, by acidification of said bath, from a salt of that hydroxy-carboxylic acid corresponding with said lactone.

6. The process as in claim 2, wherein said lactone substituted aromatic compound is formed during dyeing, by acidification of said bath, from that hydroxy-carboxyh'c acid corresponding with said lactone.

7. A process as claimed in claim 2 wherein said aromatic compound is 4,6-dimethyl cumarin.

8. A process as claimed in claim 2 wherein said aromatic compound is the lactonc of Z-hydroxynaphthalenc- I-B-propionic acid.

OTHER REFERENCES Am. Dyestuif Reporter, Nov. 13, 1950, p. 790. The Technical Bulletin of Du Pont, vol. 8, No. 2, June 1952, pp. 69-78.

Claims (1)

1. A PROCESS FOR DYEING AND PRINTING SHAPED STRUCTURES OF HYDROPHOBIC LINEAR ORGANIC HIGH POLYMERS CONTAINING ESTER GROUPS WITH DISPERSION DYESTUFFS WHICH COMPRISES DYEING SAID STRUCTURES IN THE PRESENCE OF AN AROMATIC COMPOUND CONTAINING FROM ONE TO TWO AROMATIC RINGS AND SUBSTITUTED BY FROM ONE TO TWO LACTONE RINGS HAVING FROM 5 TO 6 RING MEMBERS.