DE2330622A1 - PROCESS FOR ISOTHERMAL COLORING OF HYDROPHOBIC ORGANIC POLYESTER MATERIAL - Google Patents

Description

te. w. insane -bitui *. ο.

• IÜM3BO ti, UAUBfQKHOSRlI

Attorney's file 23 997 "* June 5, 1973

1-8239 *

CIBA-QEIQY AG Basel / Switzerland

Process for isothermal coloring of hydrophobic organic

Polyester material

The present invention relates to a method for isothermally coloring hydrophobic organic polyester material, especially of fiber material made of linear high molecular weight polyesters or cellulose triacetate, using aqueous Solutions of disperse dyes and, as an industrial product, the hydrophobic dye dyed by the new process organic polyester material.

As is well known hydrophobic organic polyester material from aqueous liquors using carefully dispersed disperse dyes by the exhaust method at the boiling point of the liquor in the presence of special tools, so-called color carriers or accelerators, or then at temperatures of 120 to 150 ⁰ C is dyed under pressure. These processes have the disadvantage that the disperse dyes have to be converted beforehand into a powdery or concentrated, aqueous form which is easily dispersible in water, according to known but lengthy and relatively expensive processes. This can be done, for example, by mechanical comminution of the disperse dyes together with suitable, advantageously anionic or nonionic dispersants and optionally other customary additives, for example protective colloids, such as dextrin, British gum or water-soluble proteins; water-soluble extenders and / or small amounts of solvents, in a kneading apparatus or a mill and, if desired

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subsequent drying, e.g. by atomization.

Also occur when dyeing hydrophobic organic polyester material from aqueous liquor on various problems, the most important of which is the dispersion stability. Minor Changes in the composition of the dye preparations, as well as small additions, for example of anionic compounds, such as electrolytes in the dye bath or mechanical factors such as shocks or vibrations can reduce the metastable state of the in Cancel water dispersed dyes. Furthermore, many finely divided disperse dyes change in aqueous liquor 70 to 140 ° C their crystal modification, such as crystal shape and crystal size. This has a detrimental effect on the dyeing Application of the dyes and leads to weak to unusable colorations.

Finally, there are many, particularly low-melting Disperse dyes not in a finely divided, dispersible Form and can therefore not be used in conventional dyeing processes are used for disperse dyes.

Belgian patent 503.684 discloses a process for dyeing fully or semi-synthetic textile fibers with dispersed dyes or acetate silk dyes, the bath with the substrate being heated to temperatures of over 100 ° C. and only then the dye dispersion is added.

A similar process is known from the article "Schnellfarbenemethode für texturierter Polyestergarn ¹¹ , Chemieffaser 20, May 1970, pages 398 ff.

In both of the cited processes, commercially available preparations of disperse dyes are used. These contain however, usually a high proportion of dispersants, in usually about 2 parts dispersant to 1 part color pigment.

A method has now been found which allows, in a simple and completely satisfactory manner, while avoiding all of the difficulties and disadvantages mentioned,

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to dye hydrophobic organic polyester material with aqueous solutions of disperse dyes, with good to excellent bath exhaustion, within shorter than the usual color times, whereby flawless, strong, even and real, e.g. dry-cleaning, sweat- and rub-fast, dyeings are obtained. The new process is that the solution at least one dispergatorarmen to dispergatorfreien disperse dye in water of 120 to 150 ⁰ C, preferably 125 to 135 ° C, into a closed dyeing apparatus, practical in a closed, pressure-resistant circulation apparatus that introduces, based on 120 to 150 ⁰ C containing heated water and hydrophobic organic polyester material and a continuous circulation of the dyeing liquor at a temperature of 120 to 150 ⁰ C, preferably 125 to 135 ° C, is finished.

The disperse dyes which can be used according to the invention can belong to a wide variety of dye classes, in particular azo, anthraquinone, nitro, methine, Styryl, azostyryl *, naphthoperinone, quinophthalone, acridone or naphthoquinone imine dyes that are free from water-solubilizing Groups are. Preferred disperse dyes are metal-free mono- or disazo dyes, nitro dyes, Acridone dyes or anthraquinone dyes.

Dyes are also understood to mean optical dispersion brighteners, e.g. brighteners from the coumarin, pyrazoline, dibenzoxazole or naphthalimide series.

Aqueous solutions of disperse dyes which can be used according to the invention are both monomolecular and genuine Solutions as well as colloidal solutions, which cause a Tyndall effect, understood.

The disperse dyes can be used, for example, as ground dye powders, which may contain additives, e.g. Extenders such as inorganic salts or dextrin; organic compounds such as ethylene glycol or sorbitols; Dispersing

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agents, such as di- (sulfonaphthyl) methane or lignosulfonate, etc., or as dye preparations, for example those in which the disperse dye has been applied to a water-insoluble carrier substance, such as diatomaceous earth, calcium carbonate powder, wood sawdust, etc., optionally by means of an adhesive will. In order to avoid the ever increasing difficulties in the treatment of waste water, low-dispersant and especially dispersant-free disperse dyes are used, whereby low-dispersant disperse dyes are understood to contain only the amount of dispersant necessary for grinding the disperse dye particles, this amount not exceeding 1 Part of dispersant to 1 \ part of disperse dye.

The amounts in which the disperse dyes are used can vary widely, depending on the depth of color desired Limits vary; in general, amounts of 0.01 to 10 percent by weight of one or more of the above have been found Disperse dyes, based on the material to be dyed, proved to be advantageous.

Fiber material made of cellulose triacetate and especially fiber material is sufficient as the hydrophobic organic polyester material linear high molecular weight esters of aromatic polycarboxylic acids with polyfunctional alcohols, for example those from Terephthalic acid and ethylene glycol or dimethylolcyclohexane, and copolymers of terephthalic acid and isophthalic acid and Ethylene glycol, but especially the difficult-to-color material made of largely oriented polyethylene glycol terephthalate, into consideration. These materials can, provided the appropriate equipment is available, in any Processing stages, e.g. in the form of flakes, sliver, yarn, textured threads, woven or knitted fabrics, as well as mixed fabrics present among themselves or with other fibers, for example as a mixed fabric made of polyester / polyamide or polyester / cotton.

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If necessary, the aqueous liquor can be used as usual Dyeing auxiliaries, advantageously in small amounts, contain such as acids, in particular an organic lower monocarboxylic acid, e.g. formic acid or acetic acid, buffer salts such as Ammonium sulfate, wetting agent or emulsifying agent.

The process according to the invention is preferably carried out in package winders or jet machines and can, for example, be carried out as follows: The disperse dye or dyes are brought in the form of a powder or preparation in water at 90 to 95 ° C and the suspension is heated in a closed, pressure-resistant, separate, However rapidly simultaneously with the dyeing machine related approach vessel to temperatures of 120 to 150 ⁰ C. in the connected pressure-tight circulation dyeing, the dyed material, which is advantageously in the form of a winding body, such as Muff ,. Cross-wound bobbin, dye tree, or as an endless web, and .Water, which is advantageously adjusted to a pH of 4 to 7, expediently 4 to 5.5, with an organic lower monocarboxylic acid such as acetic acid, with liquor circulation from the inside in brought to temperatures of 120 to 150 ⁰ C on the outside. The dye solution is then let into the dyeing apparatus as quickly as possible by opening a valve, if necessary after passing through a filter, for example to retain water-insoluble carrier substances. The two liquors advantageously have the same temperature at the time they are introduced. With further steady liquor circulation, advantageously from the inside to the outside or alternately, for example with 5-minute periods, without or with the inclusion of the batch vessel, especially in cases where the disperse dye is on a carrier substance, the dyebath is advantageous for 15 to 60 minutes 25 to 40 minutes to a temperature of 120 to 150 ⁰ C, preferably 125 to 135 ° C, maintained. After the desired depth of color has been achieved or when the dyebath is completely exhausted, the hot dye liquor is drained off and the material to be dyed is dried.

The inventive method has remarkable Advantages on: the main advantages are that above all those necessary for the fine distribution of the disperse dyes, lengthy milling operations, as well as the difficulties of dispersion stability and color unstable crystal modifications there is no need to use dyes that are not dispersible or unstable in color, and that within shorter than the usual dyeing times, Even and well-dyed dyeings can be achieved, which are extremely wet and rub-fast. There the disperse dyes are practically completely absorbed and mostly without accumulation of dirty water, the can Liquors, if necessary after passing through an activated carbon filter, easily recovered and returned to the dyeing process again, which is particularly advantageous, as there is no loss of thermal energy in the fleet. Thanks to the good exhaustion of the bath, there is no pollution the dyeing machines and the dyeings obtainable in a gentle manner with an excellent dye yield are in most cases excellent wetfastness without rinsing and / or reductive post-cleaning.

The use of dispergatorarraen to -free staining solutions can possibly improve the degree of exhaustion, as the addition of a dispersant may result in too high a solubility, which causes poorer levels of also drawing.

In particular, on linear high molecular weight polyesters one obtains colorations with a good balance of material-related Affinity differences without affecting the physical properties of the fibers.

The following examples serve to illustrate the invention without restricting it thereto. There are those Temperatures given in degrees Celsius.

example 1

0.5 g of the ground disperse dye mixture of Formulas

NH,

O ₂ N - ^ y— N = N— ^ ~ ^> R = H 25%

~~ ~~ "' ^H R = OT ₃ 75%

are introduced into 5000 ml of water at 90 to 95 ° and the suspension obtained is placed in a closed pressure-tight batch vessel a cross-bobbin dyeing machine heated to 130 °. At the same time, 500 g of textured polyethylene glycol terephthalate yarn are used as a muff and 3000 ml of water, which has been adjusted to a pH value of 5.5 with acetic acid, in a cross-coil dyeing apparatus The liquor circulation is heated from the inside to the outside to 130 °. As soon as both liquors have a temperature of 130 °, will by opening a valve, the clear dye solution from the batch vessel is quickly introduced into the cross-coil dyeing apparatus and then with further constant liquor circulation from the inside to the outside for 30 minutes on the dye liquor held at a temperature of 130 °. The colorless dye liquor is then drained off while hot and the material to be dyed is dried.

In this way a uniform and well-dyed red polyethylene glycol terephthalate yarn is obtained, excellent without the usual reductive cleaning or rinsing is wet and perfectly rubfast .. /

The drained dye liquor can be used again directly for a new dye batch.

Replacing the polyethylene glycol terephthalate yarn in the above example by appropriate amounts of cellulose triacetate yarn and otherwise proceed as described in the example, in this way one obtains colorations with similarly good results.

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Example 2

5 g of ground dispersion OCH ₃ Formulas NO ₂ / 7 ~ s \ ' O ₂ "V-" NHCOCH ₂ CH ₃ \
egg 57% R - H CH ₂ CN 43% R - CH ₂ CH ₂ OCH ₂

CH ₉ CH ₉ OCH ₉ CH ₉ CN

are introduced into 5000 ml of water at 90 to 95 ° and the suspension obtained in the closed pressure-tight batch vessel a package winder heated to 135 °. At the same time, 500 g of polyethylene glycol terephthalate spun fabric on a Carriers are rolled up, and 3000 ml of water, which has been adjusted to a pH of 5.5 with acetic acid, in a cross-coil dyeing apparatus heated to 135 ° with liquor circulation from the inside out. As soon as both liquors reach a temperature of 135 °, the clear dye solution from the preparation vessel is quickly transferred to the cross-coil dyeing apparatus by opening a valve smuggled in and then with further steady liquor circulation from the inside to the outside for 30 The dye liquor was kept at a temperature of 135 ° for minutes. The practically colorless dye liquor is then drained off while hot and dried the material to be dyed.

This is obtained without the usual reductive post-purification A uniform and well-dyed blue polyethylene glycol terephthalate spun yarn that is excellent is wet and perfectly rubfast.

If, instead of the dyes mentioned in Examples 1 and 2, one of the columns in the table below is used II, indicated dyes in the amounts indicated in column III and the rest of the procedure is as indicated in the example, in this way one also obtains strong, even and well-balanced

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wound, wetfast Ausfärburigen on polyethylene glycol terephthalate yarn or spun fabrics in the colors indicated in column IV of this table.

TABEL

II

III

IV

No.

dye

lot
G

Color shade on polyester fibers

2.1

N
^ ^{7 X}

CiH ₄ OCOCH ₂ CH ₂ -

1.8

^J 2

yellow

brilliant yellow

orange

6 "

3.8

C ₂ H ₄ OCOCH ₃

CN

Red

O ₀ N

R: = H

= N

.CH ₀ CH ₀ CN

3.3

86.5%

= NHC0CH ₃ 13.57 »

yellow-brown

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AV

II

if

)H

HO O NO,

111

5.5

6.2

JiY ι

violet

blue

Cl

Cl

Cl

• CH ₀ CH ₂ OlI

Brown

Mixture of 0.5 g of the dye in Example 1 and 1.3 g of the dye the formula given in Example 2

violet

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- Ii -

Example 12

18.6 g of a wood sawdust dye preparation according to the Swiss patent application no. 14209/71, containing 8 g of the disperse dye indicated in Example 2 Foimel are fed into a filter which is located in a secondary circuit of a circulation apparatus. While During the dyeing process, part of the dye liquor circulates continuously through the filter, with the disperse dye gradually disappearing the carrier material is removed and applied to the material to be dyed, while the carrier substance is retained by the filter will.

At the same time 400 g of a polyethylene glycol terephthalate fabric, which are rolled up on a perforated tube and 7000 ml of water that has been adjusted to pH with acetic acid of 5.5 was placed, heated to 130 ° in a circulation apparatus with liquor circulation from the inside out. As soon as the liquor has reached a temperature of 130 °, the filter with the dye preparation is opened by opening two valves included in the circuit and the dye dissolved out by the circulating aqueous liquor. Under alternating liquor circulation in periods of 5 minutes, a temperature of 130 ° is maintained for 30 minutes. The colorless dye liquor is then drained off while hot and the material to be dyed is dried.

In this way, a blue polyethylene glycol terephthalate fabric which is uniformly and well dyed through is obtained, that without the usual post-cleaning, excellently wet and flawless is rub-proof.

The wood sawdust dye preparation used in the above example was obtained as follows: 8 g of the disperse dye the formula given in Example 2, 11 g of wood sawdust, 14 g of tetrachlorethylene and 1 g of oleic acid are homogeneous mixed. The moist, loose mass obtained is then dried under vacuum at 50 °. A granular,

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dust-free dye preparation, containing 40% dye, 5% oleic acid and 55% wood sawdust.

Example 13

0.8 g of the ground, dispersant-free optical brightener 5,5'-dimethyl-bis-benzoxazolylethylene are used in 5000 ml of water entered from 90 to 95 ° and the suspension obtained in a closed pressure-tight batch vessel Cross bobbin dyeing machine heated to 130 °. At the same time, 500 g of textured polyethylene glycol terephthalate yarn are made in muff form and 3000 ml of water, which is adjusted to a pH value of 4.5 with formic acid and buffered with 16 g of ammonium sulfate, in heated to 130 ° in a cross bobbin dyeing machine. As soon as both liquors have reached the temperature of 130 °, is through Opening a valve of the optical brightener brought into solution quickly transferred from the batch vessel into the cross-bobbin dyeing apparatus and then with further steady liquor circulation kept the liquor at 130 ° from the inside to the outside for 30 minutes. After that, the withdrawn liquor drained hot and the lightened material dried.

In this way you get a white effect of excellent brilliance and purity with excellent fastness properties.

Replacing the polyethylene glycol terephthalate in the above example by a corresponding amount of cellulose triacetate yarn and otherwise proceed as described in the example white effects with similarly good results.

Example 14

5 g of a low-dispersant formulation containing 2.225 g of the dye mixture of the formulas

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J «-

N = N-CH-C-CH ₃

. I I!

HN. = C N

50%

-CH ₀ -SO ₀ -C VN = N - CH - C - CH-,

£. Δ \ - / ι π J

HN -

^ 50%

0.45 g of lignosulfonate and 2.325 g of water are analogous to the Information in Example 1 on the colors of polyethylene glycol terephthalate yarn used.

An equally solid and well-colored one is obtained golden yellow polyethylene glycol terephthalate yarn without the usual reductive cleaning or rinsing is extremely wet and perfectly rubfast. .

If the dye mixture of this low-dispersant formulation is replaced by equal amounts of the dye of the formula

I J

in this way a uniform and well-dyed orange polyethylene glycol terephthalate yarn is obtained, without the usual reductive cleaning or rinsing is extremely wet and perfectly rubfast.

ORIGINAL INSPECTED

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Claims (1)

Claims - 1. A method for isothermal dyeing hydrophobic organic polyester material, characterized in that at least one dispergatorarmen to dispergatorfreien disperse dye in water from 120 to 150 ^u C in a closed dyeing apparatus introducing the solution containing 120 to 150 ⁰ C heated water and hydrophobic organic Contains polyester material and completes the coloration at a temperature of 120 to 150 ^° C. with constant liquor circulation. 2. The method according to claim 1, characterized in that the two liquors are the same at the time of introduction Temperature between 120 and 150 ° C, especially between 125 to 135 ° C, have. 3. The method according to claims 1 and 2, characterized in that that one in the dyeing machine water, which with an organic lower monocarboxylic acid to a pH value of 4 to 7, advantageously 4 to 5.5, is used. 4 .. Process according to Claims 1 to 3, characterized in that that the disperse dye is metal-free mono- or disazo dyes, Nitro dyes, acridone dyes or anthraquinone dyes are used. 5. The method according to claims 1 to 4, characterized in that one fiber material made of linear high molecular weight esters aromatic polycarboxylic acids with polyfunctional alcohols or cellulose triacetate as a hydrophobic organic polyester material used. 6. The method according to claim 5, characterized in that polyethylene glycol terephthalate fibers are used. 309883/1283 7. The method according to claims 1 to 6, characterized in that that the hydrophobic organic polyester material is used in the form of a wrapped body or an endless web of material. 8. The method according to claim 1, characterized in that the drawn-out dye bath is fed back to the dyeing process. 9. The colored according to claims 1 to 8 hydrophobic organic polyester material, especially linear high molecular weight polyester material. 5/24/73
Db "/ sh 309883/1283